Methods for sol-gel polymerization in absence of solvent and creation of tunable carbon structure from same

ABSTRACT

The present application is directed to methods for solvent-free preparation of polymers and their subsequent processing into activated carbon materials. These methods unexpectedly demonstrate ability to tune pore structure in the polymer gel and carbon produced there from, while also providing distinct advantages over the current art.

BACKGROUND

Technical Field

The present invention generally relates to novel methods for preparingpolymeric resin materials without the use of solvent, and preparation ofcarbon materials from the same.

Description of the Related Art

Activated carbon is commonly employed in electrical storage anddistribution devices. The surface area, conductivity and porosity ofactivated carbon allows for the design of electrical devices havingdesirable electrochemical performance. Electric double-layer capacitors(EDLCs or “ultracapacitors”) are an example of such devices. EDLCs oftenhave electrodes prepared from an activated carbon material and asuitable electrolyte, and have an extremely high energy density comparedto more common capacitors. Typical uses for EDLCs include energy storageand distribution in devices requiring short bursts of power for datatransmissions, or peak-power functions such as wireless modems, mobilephones, digital cameras and other hand-held electronic devices. EDLCsare also commonly used in electric vehicles such as electric cars,trains, buses and the like.

Batteries are another common energy storage and distribution devicewhich often contain an activated carbon material (e.g., as anodematerial, current collector, or conductivity enhancer). For example,lithium/carbon batteries having a carbonaceous anode intercalated withlithium represent a promising energy storage device. Other types ofcarbon-containing batteries include lithium air batteries, which useporous carbon as the current collector for the air electrode, and leadacid batteries which often include carbon additives in either the anodeor cathode. Batteries are employed in any number of electronic devicesrequiring low current density electrical power (as compared to an EDLC'shigh current density).

One known limitation of EDLCs and carbon-based batteries is decreasedperformance at high-temperature, high voltage operation, repeatedcharge/discharge cycles and/or upon aging. This decreased performancehas been attributed, at least in part, to electrolyte impurity orimpurities in the carbon electrode itself, causing breakdown of theelectrode at the electrolyte/electrode interface. Thus, it has beensuggested that EDLCs and/or batteries comprising electrodes preparedfrom higher purity carbon materials could be operated at higher voltagesand for longer periods of time at higher temperatures than existingdevices.

In addition to purity, another known limitation of carbon-containingelectrical devices is the pore structure of the activated carbon itself.While activated carbon materials typically comprise high porosity, thepore size distribution is not optimized for use in electrical energystorage and distribution devices. Such optimization may include a blendof both micropores and mesopores. Additionally in some applications ahigh surface area carbon may be desirable, while in others a low surfaceare material is preferred. Idealized pore size distributions canmaximize performance attributes including but not limited to, increasedion mobility (i.e., lower resistance), increased power density, improvedvolumetric capacitance, increased cycle life efficiency of devicesprepared from the optimized carbon materials.

One common method for producing carbon materials is to pyrolyze anexisting carbon-containing material (e.g., coconut fibers or tirerubber). This results in a char with relatively low surface area whichcan subsequently be over-activated to produce a material with thesurface area and porosity necessary for the desired application. Such anapproach is inherently limited by the existing structure of theprecursor material, and typically results in a carbon material havingnon-optimized pore structure and an ash content (e.g., metal impurities)of 1% or higher.

Activated carbon materials can also be prepared by chemical activation.For example, treatment of a carbon-containing material with an acid,base or salt (e.g., phosphoric acid, potassium hydroxide, sodiumhydroxide, zinc chloride, etc.) followed by heating results in anactivated carbon material. However, such chemical activation alsoproduces an activated carbon material not suitable for use in highperformance electrical devices.

Another approach for producing high surface area activated carbonmaterials is to prepare a synthetic polymer from carbon-containingorganic building blocks (e.g., a polymer gel). As with the existingorganic materials, the synthetically prepared polymers are pyrolyzed andactivated to produce an activated carbon material. To this end, thecurrent approach is to conduct the polymerization, for example creationof sol-gel polymer, in the presence of one or more solvents. Uponremoval of solvents, the dried gel exhibits a pore structure as a resultof the voids left behind by the removed solvent. Solvents do not becomepart of the carbon network, therefore this traditional approach resultsin lower carbon yield per mass of precursor materials, and higherprocessing costs since solvent removal is an energy-intensive process

Accordingly, a polymer manufacturing approach that improving carbonyield and reduce carbon processing costs is needed. The presentinvention, which provides for tunable pore structures contrary tocurrent teachings in the art, fulfills these needs and provides furtherrelated advantages.

BRIEF SUMMARY

In general terms, the current invention is directed to novel methods forpreparing polymers and their further processing into carbon materialscomprising tunable pore structure. The methods generally comprisepreparation of a mixture of solid polymer precursors and crosslinkingagents, blending in the solid form, and exposure to sufficientconditions to promote polymerization. The process can be carried out invarious modes to create polymer particles of various sizes andgeometries. The resulting polymer can then optionally be converted tocarbon materials by any number of post-processing procedures, includingpyrolysis and/or activation.

Prior art teaches that solvents are required (i.e., sol-gelpolymerization) to produce polymers suitable for manufacturing tunablecarbon materials. The present inventors have discovered novelpolymerization methodologies with little or no solvent employed thatunexpected allowed for preparation of tunable carbon pore structures.

Solvent-free polymer gels and carbon materials prepared according to thedisclosed methods are also provided. Electrodes and devices comprisingthe carbon materials are also provided. These and other aspects of theinvention will be apparent upon reference to the following detaileddescription. To this end, various references are set forth herein whichdescribe in more detail certain background information, procedures,compounds and/or compositions, and are each hereby incorporated byreference in their entirety.

Accordingly, in some embodiments the present invention provides a methodfor preparing a polymer, the method comprising physical blending of amixture of particles comprising polymer precursors and aging the mixtureat a temperature and for a time sufficient for the one or more polymerprecursors to react with each other and form a polymer gel, and whereinthe mixture comprises less than 10% solvent by weight. For example, insome embodiments the mixture comprises less than 1% solvent by weight.In other embodiments, the mixture comprises less than 0.1% solvent byweight.

In different embodiments of the foregoing method, the temperature is ator above the glass transition temperature of one or more species ofpolymer precursor particles.

In still other embodiments, the temperature is at or above the meltingtemperature of one or more species of polymer precursor particles. Inother embodiments, the temperature is at or above 30 C below the meltingtemperature of one or more species of polymer precursor particles.

In certain other embodiments of the foregoing, the polymer precursorsare selected from an amine-containing compound, an alcohol-containingcompound and a carbonyl-containing compound. In other embodiments, thepolymer precursors are selected from an alcohol, a phenol compound, apolyalcohol, a sugar, an alkyl amine, an aromatic amine, an aldehyde, aketone, a carboxylic acid, an ester, melamine, a urea, an acid halideand an isocyanate. In more specific embodiments, the phenolic compoundis phenol, resorcinol, naphthol, bisphenol A, or any combinationthereof. In other embodiments, the sugar is fructose, sucrose, glucose,or any combination thereof. In some embodiments, the carboxylic acid isacetic acid, formic acid, oxalic acid, lactic acid, citric acid,cyanuric acid, or any combination thereof.

In some embodiments, the polymer precursors further comprisehexamethylenetetramine. For example, in some embodiments the polymerprecursors comprise hexamethylenetetramine and bisphenol A present at amole ratio between 0.05:1 to 5:1.

In other embodiments, the method further comprises pyrolyzing thesolvent free polymer gel particles in an inert atmosphere attemperatures ranging from 500° C. to 2400° C. to obtain pyrolyzedpolymer gel particles.

In other embodiments, the method further comprises activating thepyrolyzed polymer gel particles to obtain activated polymer gelparticles by a method comprising contacting the pyrolyzed polymer gelparticles with an atmosphere comprising carbon dioxide, carbon monoxide,steam, oxygen or combinations thereof at a temperature may ranging from800° C. to 1300° C.

In other embodiments, the invention provides a carbon material having amaximum theoretical capacitance of greater than 26 F/cm³, wherein thecapacitance is measured at a current density of 0.5 Amp/g employing anelectrolyte comprising tetraethylammonium tetrafluoroborane inacetonitrile. In some embodiments, the maximum theoretical capacitanceis greater than 27 F/cm³. In other embodiments, the maximum theoreticalcapacitance is greater than 28 F/cm³. In still more embodiments, themaximum theoretical capacitance is greater than 29 F/cm³.

In various other embodiments of the foregoing carbon material, thenitrogen content is 1-8%.

In some embodiments, an electrode comprising the foregoing carbonmaterial is provided.

Also provided in various embodiments is an electrode comprising carbon,wherein the carbon comprises a maximum theoretical capacitance ofgreater than 25 F/cm³, wherein the capacitance is measured afterincubation at 3 V and 65 C for 12 h, and at a current density of 0.5Amp/g employing an electrolyte comprising tetraethylammoniumtetrafluoroborane in acetonitrile.

In different embodiments, the invention is directed to an electricalenergy storage device comprising the foregoing electrode. In someembodiments, the electrical energy storage device is an electric doublelayer capacitor. In other embodiments, the electrical energy storagedevice is a battery. In still other embodiments, the electrical energystorage device is a lithium/carbon battery, zinc/carbon battery, lithiumair battery or lead acid battery.

In other embodiments, a solvent-free process for producing a carbonwithin a reactor is provided, wherein the process comprises:

(a) reducing the particle size of solid polymer precursor materials,either within or external to the reactor;

(b) introducing particles of polymer precursor materials into thereactor;

(c) thorough blending of particles within the reactor or reactor feedingmechanism;

(d) incubating at a temperature, residence time, and atmosphere suitableto induce polymerization; and

(e) incubating at a temperature, residence time, and atmosphere suitableto induce pyrolysis, activation, reduction of surface functional groups,or any combination thereof.

A solvent-free process for increasing the nitrogen content ofcarbonaceous material is also provided in a different embodiments,wherein the process comprises:

(a) physically mixing carbonaceous material and a compound capable ofdecomposing to formaldehyde and ammonia;

(b) incubating at a temperature, residence time, and atmosphere suitableto induce nitrogen incorporation; and

(c) incubating at a temperature, residence time, and atmosphere suitableto remove unreacted components.

In some embodiments of the foregoing process, the compound ishexamethylenetetramine.

Other electrodes comprising carbon are also provided, wherein the carboncomprises a BF of 0.1 or lower, wherein the BF is measured employing anelectrolyte comprising tetraethylammonium tetrafluoroborane inacetonitrile.

In still more embodiments, an electrode comprising carbon is provided,wherein the carbon comprises a BF of 0.1 or lower, wherein thecapacitance is measured after incubation at 3 V and 65 C for 12 hemploying an electrolyte comprising tetraethylammonium tetrafluoroboranein acetonitrile.

These and other aspects of the invention will be apparent upon referenceto the following detailed description. To this end, various referencesare set forth herein which describe in more detail certain backgroundinformation, procedures, compounds and/or compositions, and are eachhereby incorporated by reference in their entirety.

BRIEF DESCRIPTION OF THE DRAWINGS

In the figures, identical reference numbers identify similar elements.The sizes and relative positions of elements in the figures are notnecessarily drawn to scale and some of these elements are arbitrarilyenlarged and positioned to improve figure legibility. Further, theparticular shapes of the elements as drawn are not intended to conveyany information regarding the actual shape of the particular elements,and have been solely selected for ease of recognition in the figures.

FIGS. 1-14 are FTIR spectra of exemplary samples.

FIGS. 15A and 15B present incremental pore volume and pore width data,respectively.

FIGS. 16A and 16B are plots showing incremental pore volume and porewidth, respectively.

FIG. 17 is an FTIR spectrum of a glucose resin.

FIG. 18 shows a voltage profile of carbon produced from a glucose resin.

FIG. 19 is an FTIR spectrum of a fructose cured resin.

FIG. 20 present voltage profile data for carbon produced from fructoseresin.

FIG. 21 is a plot of a nitrogen sorption isotherm.

FIG. 22 presents a DFT pore volume distribution as calculated from anitrogen sorption isotherm.

FIG. 23 depicts volumetric capacitance of carbon samples 20-1, 20-3 andcontrol carbon (YP-50) at baseline.

FIG. 24 depicts volumetric capacitance of carbon samples 20-1, 20-3 andcontrol carbon (YP-50) after 3V voltage hold for 12 h at 65 C.

FIG. 25 depicts maximum theoretical volumetric capacitance for variouscarbons produced via solvent-free process as a function of surface area.

FIG. 26 depicts gravimetric capacitance for various carbons produced viasolvent-free process as a function of total pore volume.

FIG. 27 depicts the DFT pore volume distribution for the carbon ofExample 26.

FIG. 28 depicts the DFT pore volume distribution for the carbon ofExample 27.

FIG. 29A-D depicts cyclic voltammetry data for an exemplary carbonaccording to an embodiment of the present invention and a commerciallyavailable carbon.

DETAILED DESCRIPTION

In the following description, certain specific details are set forth inorder to provide a thorough understanding of various embodiments.However, one skilled in the art will understand that the invention maybe practiced without these details. In other instances, well-knownstructures have not been shown or described in detail to avoidunnecessarily obscuring descriptions of the embodiments. Unless thecontext requires otherwise, throughout the specification and claimswhich follow, the word “comprise” and variations thereof, such as,“comprises” and “comprising” are to be construed in an open, inclusivesense, that is, as “including, but not limited to.” Further, headingsprovided herein are for convenience only and do not interpret the scopeor meaning of the claimed invention.

Reference throughout this specification to “one embodiment” or “anembodiment” means that a particular feature, structure or characteristicdescribed in connection with the embodiment is included in at least oneembodiment. Thus, the appearances of the phrases “in one embodiment” or“in an embodiment” in various places throughout this specification arenot necessarily all referring to the same embodiment. Furthermore, theparticular features, structures, or characteristics may be combined inany suitable manner in one or more embodiments. Also, as used in thisspecification and the appended claims, the singular forms “a,” “an,” and“the” include plural referents unless the content clearly dictatesotherwise. It should also be noted that the term “or” is generallyemployed in its sense including “and/or” unless the content clearlydictates otherwise.

Definitions

As used herein, and unless the context dictates otherwise, the followingterms have the meanings as specified below.

“Carbon material” refers to a material or substance comprisedsubstantially of carbon (e.g., >90%, >95%, greater than 99% or greaterthan 99.9% carbon on a weight basis). Carbon materials include ultrapureas well as amorphous and crystalline carbon materials. Some carbonmaterials may comprise electrochemical modifiers (e.g. Si or N) tomodify (e.g., enhance) device performance as described in more detailbelow. Examples of carbon materials include, but are not limited to,activated carbon, pyrolyzed dried polymer gels, pyrolyzed polymercryogels, pyrolyzed polymer xerogels, pyrolyzed polymer aerogels,activated dried polymer gels, activated polymer cryogels, activatedpolymer xerogels, activated polymer aerogels and the like.

“Electrochemical modifier” refers to any chemical element, compoundcomprising a chemical element or any combination of different chemicalelements and compounds which modifies (e.g., enhances or decreases) theelectrochemical performance of a carbon material. Electrochemicalmodifiers can change (increase or decrease) the resistance, capacity,power performance, stability and other properties of a carbon material.Electrochemical modifiers generally impart a desired electrochemicaleffect. In contrast, an impurity in a carbon material is generallyundesired and tends to degrade, rather than enhance, the electrochemicalperformance of the carbon material. Examples of electrochemicalmodifiers within the context of the present disclosure include, but arenot limited to, elements, and compounds or oxides comprising elements,in groups 12-15 of the periodic table, other elements such as sulfur,tungsten and silver and combinations thereof. For example,electrochemical modifiers include, but are not limited to, lead, tin,antimony, bismuth, arsenic, tungsten, silver, zinc, cadmium, indium,silicon and combinations thereof as well as oxides of the same andcompounds comprising the same.

“Group 12” elements include zinc (Zn), cadmium (Cd), mercury (Hg), andcopernicium (Cn).

“Group 13” elements include boron (B), aluminum (Al), gallium (Ga),indium (In) and thallium (Tl).

“Group 14” elements include carbon (C), silicon (Si), germanium (Ge),tin (Sn) and lead (Pb).

“Group 15” elements include nitrogen (N), phosphorous (P), arsenic (As),antimony (Sb) and bismuth (Bi).

“Amorphous” refers to a material, for example an amorphous carbonmaterial, whose constituent atoms, molecules, or ions are arrangedrandomly without a regular repeating pattern. Amorphous materials mayhave some localized crystallinity (i.e., regularity) but lack long-rangeorder of the positions of the atoms. Pyrolyzed and/or activated carbonmaterials are generally amorphous.

“Crystalline” refers to a material whose constituent atoms, molecules,or ions are arranged in an orderly repeating pattern. Examples ofcrystalline carbon materials include, but are not limited to, diamondand graphene.

“Synthetic” refers to a substance which has been prepared by chemicalmeans rather than from a natural source. For example, a synthetic carbonmaterial is one which is synthesized from precursor materials and is notisolated from natural sources.

“Impurity” or “impurity element” refers to an undesired foreignsubstance (e.g., a chemical element) within a material which differsfrom the chemical composition of the base material. For example, animpurity in a carbon material refers to any element or combination ofelements, other than carbon, which is present in the carbon material.Impurity levels are typically expressed in parts per million (ppm).

“PIXE impurity” or “PIXE element” is any impurity element having anatomic number ranging from 11 to 92 (i.e., from sodium to uranium). Thephrases “total PIXE impurity content” and “total PIXE impurity level”both refer to the sum of all PIXE impurities present in a sample, forexample, a polymer gel or a carbon material. PIXE impurityconcentrations and identities may be determined by proton induced x-rayemission (PIXE).

“Ultrapure” refers to a substance having a total PIXE impurity contentof less than 0.050%. For example, an “ultrapure carbon material” is acarbon material having a total PIXE impurity content of less than 0.050%(i.e., 500 ppm).

“Ash content” refers to the nonvolatile inorganic matter which remainsafter subjecting a substance to a high decomposition temperature.Herein, the ash content of a carbon material is calculated from thetotal PIXE impurity content as measured by proton induced x-rayemission, assuming that nonvolatile elements are completely converted toexpected combustion products (i.e., oxides).

“Polymer” refers to a macromolecule comprised of one or more structuralrepeating units.

“Synthetic polymer precursor material” or “polymer precursor” refers tocompounds used in the preparation of a synthetic polymer. Polymerprecursors are generally compounds which may combined (i.e., reacted)with other compounds to form a polymer, for example a condensationpolymer. Polymer precursors include monomers, as well as monomers whichhave been partially polymerized (i.e., dimers, oligomers, etc.).Generally, the polymer precursors are selected from aromatic oraliphatic alcohols or amines and carbonyl containing compounds (e.g.,carboxylic acids, ketones, aledehydes, isocyanates, ureas, amides, acidhalides, esters, activated carbonyl-containing compounds and the like).Examples of polymer precursors that can be used in certain embodimentsof the preparations disclosed herein include, but are not limited to,aldehydes (i.e., HC(═O)R, where R is an organic group), such as forexample, methanal (formaldehyde); ethanal (acetaldehyde); propanal(propionaldehyde); butanal (butyraldehyde); glucose; benzaldehyde andcinnamaldehyde. Other exemplary polymer precursors include, but are notlimited to, phenolic compounds such as phenol and polyhydroxy benzenes,such as dihydroxy or trihydroxy benzenes, for example, resorcinol (i.e.,1,3-dihydroxy benzene), catechol, hydroquinone, naphthol, andphloroglucinol. Amines, such as melamine, and urea may also be used.Mixtures of two or more polyhydroxy benzenes are also contemplatedwithin the meaning of polymer precursor. Yet another example of a usefulpolymer precursor in this regard is cyanuric acid and related compoundscomprising both carboxylic groups and anime groups.

“Condensation polymer” is a polymer that results from reaction of one ormore polymer precursors with elimination of a small molecule (e.g.water). Exemplary condensation polymers include, but are not limited to,polymers formed from reaction of an alcohol or amine with a carbonylcontaining compound.

“Monolithic” refers to a solid, three-dimensional structure that is notparticulate in nature.

“Sol” refers to a colloidal suspension of precursor particles (e.g.,polymer precursors), and the term “gel” refers to a wetthree-dimensional porous network obtained by condensation or reaction ofthe precursor particles.

“Polymer gel” refers to a gel in which the network component is apolymer; generally a polymer gel is a wet (aqueous or non-aqueous based)three-dimensional structure comprised of a polymer formed from syntheticprecursors or polymer precursors.

“Sol gel” refers to a sub-class of polymer gel where the polymer is acolloidal suspension that forms a wet three-dimensional porous networkobtained by reaction of the polymer precursors.

“Polymer hydrogel” or “hydrogel” refers to a subclass of polymer gel orgel wherein the solvent for the synthetic precursors or monomers iswater or mixtures of water and one or more water-miscible solvent.

“RF polymer hydrogel” refers to a sub-class of polymer gel wherein thepolymer was formed from the catalyzed reaction of resorcinol andformaldehyde in water or mixtures of water and one or morewater-miscible solvent.

“Continuous Phase” refers to the liquid phase in which thepolymerization components (i.e., polymer precursors, catalyst, acid,etc.) are dissolved, suspended and/or emulsified. Continuous phases maybe either hydrophilic or hydrophobic and have varying viscosities.Mixtures of two or more different continuous phases are alsocontemplated. Any number of different liquids (e.g., solvents) may beemployed within the context of the invention as described in more detailherein.

“Acid” refers to any substance that is capable of lowering the pH of asolution. Acids include Arrhenius, Brønsted and Lewis acids. A “solidacid” refers to a dried or granular compound that yields an acidicsolution when dissolved in a solvent. The term “acidic” means having theproperties of an acid.

“Base” refers to any substance that is capable of raising the pH of asolution. Bases include Arrhenius, Brønsted and Lewis bases. A “solidbase” refers to a dried or granular compound that yields basic solutionwhen dissolved in a solvent. The term “basic” means having theproperties of a base.

“Miscible” refers to the property of a mixture wherein the mixture formsa single phase over certain ranges of temperature, pressure, andcomposition.

“Catalyst” is a substance which alters the rate of a chemical reaction.Catalysts participate in a reaction in a cyclic fashion such that thecatalyst is cyclically regenerated. The present disclosure contemplatescatalysts which are sodium free. The catalyst used in the preparation ofa polymer gel (e.g., an ultrapure polymer gel) as described herein canbe any compound that facilitates the polymerization of the polymerprecursors to form an ultrapure polymer gel. A “volatile catalyst” is acatalyst which has a tendency to vaporize at or below atmosphericpressure. Exemplary volatile catalysts include, but are not limited to,ammoniums salts, such as ammonium bicarbonate, ammonium carbonate,ammonium hydroxide, and combinations thereof.

“Solvent” refers to a substance which dissolves or suspends reactants(e.g., ultrapure polymer precursors) and provides a medium in which areaction may occur. Examples of solvents useful in the preparation ofthe gels, ultrapure polymer gels, ultrapure synthetic carbon materialsand ultrapure synthetic amorphous carbon materials disclosed hereininclude, but are not limited to, water, alcohols and mixtures thereof.Exemplary alcohols include ethanol, t-butanol, methanol and mixturesthereof. Such solvents are useful for dissolution of the syntheticultrapure polymer precursor materials, for example dissolution of aphenolic or aldehyde compound. In addition, in some processes suchsolvents are employed for solvent exchange in a polymer hydrogel (priorto freezing and drying), wherein the solvent from the polymerization ofthe precursors, for example, resorcinol and formaldehyde, is exchangedfor a pure alcohol. In one embodiment of the present application, acryogel is prepared by a process that does not include solvent exchange.

“Dried gel” or “dried polymer gel” refers to a gel or polymer gel,respectively, from which the solvent, generally water, or mixture ofwater and one or more water-miscible solvents, has been substantiallyremoved.

“Pyrolyzed dried polymer gel” refers to a dried polymer gel which hasbeen pyrolyzed but not yet activated, while an “activated dried polymergel” refers to a dried polymer gel which has been activated.

“Cryogel” refers to a dried gel that has been dried by freeze drying.

“RF cryogel” refers to a dried gel that has been dried by freeze dryingwherein the gel was formed from the catalyzed reaction of resorcinol andformaldehyde.

“Pyrolyzed cryogel” is a cryogel that has been pyrolyzed but not yetactivated.

“Activated cryogel” is a cryogel which has been activated to obtainactivated carbon material.

“Xerogel” refers to a dried gel that has been dried by air drying, forexample, at or below atmospheric pressure.

“Pyrolyzed xerogel” is a xerogel that has been pyrolyzed but not yetactivated.

“Activated xerogel” is a xerogel which has been activated to obtainactivated carbon material.

“Aerogel” refers to a dried gel that has been dried by supercriticaldrying, for example, using supercritical carbon dioxide.

“Pyrolyzed aerogel” is an aerogel that has been pyrolyzed but not yetactivated.

“Activated aerogel” is an aerogel which has been activated to obtainactivated carbon material.

“Organic extraction solvent” refers to an organic solvent added to apolymer hydrogel after polymerization of the polymer precursors hasbegun, generally after polymerization of the polymer hydrogel iscomplete.

“Rapid multi-directional freezing” refers to the process of freezing apolymer gel by creating polymer gel particles from a monolithic polymergel, and subjecting said polymer gel particles to a suitably coldmedium. The cold medium can be, for example, liquid nitrogen, nitrogengas, or solid carbon dioxide. During rapid multi-directional freezingnucleation of ice dominates over ice crystal growth. The suitably coldmedium can be, for example, a gas, liquid, or solid with a temperaturebelow about −10° C. Alternatively, the suitably cold medium can be agas, liquid, or solid with a temperature below about −20° C.Alternatively, the suitably cold medium can be a gas, liquid, or solidwith a temperature below about −30° C.

“Activate” and “activation” each refer to the process of heating a rawmaterial or carbonized/pyrolyzed substance at an activation dwelltemperature during exposure to oxidizing atmospheres (e.g., carbondioxide, oxygen, steam or combinations thereof) to produce an“activated” substance (e.g., activated cryogel or activated carbonmaterial). The activation process generally results in a stripping awayof the surface of the particles, resulting in an increased surface area.Alternatively, activation can be accomplished by chemical means, forexample, by impregnation of carbon-containing precursor materials withchemicals such as acids like phosphoric acid or bases like potassiumhydroxide, sodium hydroxide or salts like zinc chloride, followed bycarbonization. “Activated” refers to a material or substance, forexample a carbon material, which has undergone the process ofactivation.

“Carbonizing”, “pyrolyzing”, “carbonization” and “pyrolysis” each referto the process of heating a carbon-containing substance at a pyrolysisdwell temperature in an inert atmosphere (e.g., argon, nitrogen orcombinations thereof) or in a vacuum such that the targeted materialcollected at the end of the process is primarily carbon. “Pyrolyzed”refers to a material or substance, for example a carbon material, whichhas undergone the process of pyrolysis.

“Dwell temperature” refers to the temperature of the furnace during theportion of a process which is reserved for maintaining a relativelyconstant temperature (i.e., neither increasing nor decreasing thetemperature). For example, the pyrolysis dwell temperature refers to therelatively constant temperature of the furnace during pyrolysis, and theactivation dwell temperature refers to the relatively constanttemperature of the furnace during activation.

“Pore” refers to an opening or depression in the surface, or a tunnel ina carbon material, such as for example activated carbon, pyrolyzed driedpolymer gels, pyrolyzed polymer cryogels, pyrolyzed polymer xerogels,pyrolyzed polymer aerogels, activated dried polymer gels, activatedpolymer cryogels, activated polymer xerogels, activated polymer aerogelsand the like. A pore can be a single tunnel or connected to othertunnels in a continuous network throughout the structure.

“Pore structure” refers to the layout of the surface of the internalpores within a carbon material, such as an activated carbon material.Components of the pore structure include pore size, pore volume, surfacearea, density, pore size distribution and pore length. Generally thepore structure of an activated carbon material comprises micropores andmesopores. For example, in certain embodiments the ratio of microporesto mesopores is optimized for enhanced electrochemical performance.

“Mesopore” refers to a pore having a diameter ranging from 2 nanometersto 50 nanometers while the term “micropore” refers to a pore having adiameter less than 2 nanometers.

“Macropore” refers to a pore having a diameter greater than 50 nm.

“Surface area” refers to the total specific surface area of a substancemeasurable by the BET technique. Surface area is typically expressed inunits of m²/g. The BET (Brunauer/Emmett/Teller) technique employs aninert gas, for example nitrogen, to measure the amount of gas adsorbedon a material and is commonly used in the art to determine theaccessible surface area of materials.

“Connected” when used in reference to mesopores and micropores refers tothe spatial orientation of such pores.

“Effective length” refers to the portion of the length of the pore thatis of sufficient diameter such that it is available to accept salt ionsfrom the electrolyte.

“Electrode” refers to a conductor through which electricity enters orleaves an object, substance or region.

“Binder” refers to a material capable of holding individual particles ofa substance (e.g., a carbon material) together such that after mixing abinder and the particles together the resulting mixture can be formedinto sheets, pellets, disks or other shapes. In certain embodiments, anelectrode may comprise the disclosed carbon materials and a binder.Non-exclusive examples of binders include fluoro polymers, such as, forexample, PTFE (polytetrafluoroethylene, Teflon), PFA (perfluoroalkoxypolymer resin, also known as Teflon), FEP (fluorinated ethylenepropylene, also known as Teflon), ETFE (polyethylenetetrafluoroethylene,sold as Tefzel and Fluon), PVF (polyvinyl fluoride, sold as Tedlar),ECTFE (polyethylenechlorotrifluoroethylene, sold as Halar), PVDF(polyvinylidene fluoride, sold as Kynar), PCTFE(polychlorotrifluoroethylene, sold as Kel-F and CTFE), trifluoroethanoland combinations thereof.

“Inert” refers to a material that is not active in the electrolyte of anelectrical energy storage device, that is it does not absorb asignificant amount of ions or change chemically, e.g., degrade.

“Conductive” refers to the ability of a material to conduct electronsthrough transmission of loosely held valence electrons.

“Current collector” refers to a part of an electrical energy storageand/or distribution device which provides an electrical connection tofacilitate the flow of electricity in to, or out of, the device. Currentcollectors often comprise metal and/or other conductive materials andmay be used as a backing for electrodes to facilitate the flow ofelectricity to and from the electrode.

“Electrolyte” means a substance containing free ions such that thesubstance is electrically conductive. Electrolytes are commonly employedin electrical energy storage devices. Examples of electrolytes include,but are not limited to, solvents such as propylene carbonate, ethylenecarbonate, butylene carbonate, dimethyl carbonate, methyl ethylcarbonate, diethyl carbonate, sulfolane, methylsulfolane, acetonitrileor mixtures thereof in combination with solutes such astetralkylammonium salts such as TEA TFB (tetraethylammoniumtetrafluoroborate), MTEATFB (methyltriethylammonium tetrafluoroborate),EMITFB (1-ethyl-3-methylimidazolium tetrafluoroborate),tetraethylammonium, triethylammonium based salts or mixtures thereof. Insome embodiments, the electrolyte can be a water-based acid orwater-based base electrolyte such as mild aqueous sulfuric acid oraqueous potassium hydroxide.

“Solvent-free” mixture refers to a mixture of solid or liquid components(for instance mixture of polymer precursors and cross linking agents)that does not comprise an added liquid at a level that dissolves ordilutes one or more of the solid or liquid components.

“Maximum theoretical volumetric capacitance” is the volumetriccapacitance of carbon as calculated as the F/g divided by the totalvolume which is the sum of carbon skeletal volume (generally assumed tobe 0.439 cm3/g) and the total pore volume as measured by nitrogensorption. Unless otherwise specified, electrochemical data presentedherein (including the maximum theoretical volumetric capacitance) arebased on carbon electrode comprised of 92% active carbon, 5%conductivity enhancer and 3% binder at a current density of 0.5 Amp/gemploying an electrolyte comprising tetraethylammonium tetrafluoroboranein acetonitrile.

A. Preparation of Polymer Gels and Carbon Materials

The structure, properties and methods for making various carbonmaterials and polymer gels are described herein and in U.S. Pub. Nos.2007/0113735; 2011/0028599; 2011/0002086; 2011/0223494; 2011/0159375;2012/0081838; 2012/0202033; 2013/0004841; 2013/0252082 and 2013/0280601,the full disclosures of which are hereby incorporated by reference intheir entireties.

The disclosed preparation of carbon materials represents a number ofadvances over currently known methods for preparation of carbonmaterials. For example, tunable carbon materials have traditionally beenmade by producing carbon materials from synthetic polymers produced inpresence of one or more solvent (i.e., sol-gel polymers). Thesolvent-containing polymer must then be dried to remove the solvents,and the dried polymer gel is subsequently pyrolyzed and/or activatedinto carbon materials. Such procedures suffer from a number ofdrawbacks.

First, the removal of solvent is a cost- and time-intensive process. Thecurrent art teaches that rapid freezing and removal of frozen solventvia sublimation under vacuum is a preferred mode to provide tunabilityof pore structure. This rapid freeing and drying requires very lowtemperature and very low vacuum, which in turn require a large amount ofenergy. The drying process can take from hours to days to complete.

Second, the solvent does not become incorporated into the carbonmaterial, and therefore lowers the yield of carbon per unit mass ofpolymer gel processed. For example, the solvent can be present at alevel of more than 30% of the total mass of polymer to be processed intocarbon, for example more than 40% of the total mass of polymer to beprocessed. more than 50% of the total mass of polymer to be processed,more than 60% of the total mass of polymer to be processed, more than70% of the total mass of polymer to be processed, more than 80% of thetotal mass of polymer to be processed, more than 90% of the total massof polymer to be processed. Without being bound by theory, a pyrolyzedcarbon yield from a polymeric material can be about 50%. Accordingly,the ratio of pyrolyzed carbon produced per unit mass of polymerprocessed can be greater than about 3, greater than about 4, greaterthan about 5, greater than about 7, greater than about 10, greater thanabout 20, greater than about 200. The pyrolyzed carbon can be activated,and the ratio of activated carbon to polymer processed is higher thanthe ratio of pyrolyzed carbon to polymer processed, depending on thelevel of activation desired. Without being bound by theory, a activatedcarbon yield from a pyrolyzed carbon material can be about 50%.Accordingly, the ratio of activated carbon produced per unit mass ofpolymer processed can be greater than about 6, greater than about 8,greater than about 10, greater than about 14, greater than about 20,greater than about 40, greater than about 400.

Even owing the disadvantages above, production of carbon from sol gelpolymer networks is attractive because the employment of the solventallows modulation of concentration of various components (polymerprecursors, acids, bases, co-solvents and the like) which is taught inthe prior art to provide modulation of pore structure in the driedpolymer, pyrolyzed polymer, and/or pyrolyzed and activated polymer.

The current art therefore teaches away from conducting polymerization inthe absence of solvent to produce carbon with tunable structures.Unexpectedly, the current invention demonstrates tunability of porestructures in carbons derived from polymers produced in absence ofsolvent.

1. Preparation of Polymer Gels

As noted above, one embodiment of the present disclosure is a method forpreparing carbon materials following a polymerization process in theabsence of solvent. In one embodiment, the method comprises heatingpolymer gel particles that were formed in absence of solvent to obtain acarbon material, wherein the polymer has been prepared by a processcomprising:

a) blending a mixture of solid and/or liquid polymer precursors; and

b) aging the mixture at a temperature and for a time sufficient toproduce a solvent-free polymer network; and

c) pyrolysis or pyrolysis and activation of the solvent-free polymernetwork to produce tunable carbon

In some embodiments, the solvent can be present at a level of less than80% of the total mass of polymer to be processed into carbon, forexample less than 70% of the total mass of polymer to be processed, lessthan 60% of the total mass of polymer to be processed, less than 50% ofthe total mass of polymer to be processed, less than 40% of the totalmass of polymer to be processed, less than 30% of the total mass ofpolymer to be processed, less than 20% of the total mass of polymer tobe processed, less than 10% of the total mass of polymer to beprocessed, less than 1% of the total mass of polymer to be processed,less than 0.1% of the total mass of polymer to be processed, less than0.01% of the total mass of polymer to be processed. Without being boundby theory, a pyrolyzed carbon yield from a polymeric material can beabout 50%. Accordingly, the ratio of pyrolyzed carbon produced per unitmass of polymer processed can be less than about 10, less than about 7,less than about 5, less than about 4, less than about 3, less than about2.5, less than about 2.1. In some embodiments, the ratio of pyrolyzedcarbon produced per unit mass of polymer processed is about 2. In someembodiments, the ratio of pyrolyzed carbon produced per unit mass ofpolymer processed is less than 2.

The pyrolyzed carbon can be activated, and the ratio of activated carbonto polymer processed is higher than the ratio of pyrolyzed carbon topolymer processed, depending on the level of activation desired. Withoutbeing bound by theory, a activated carbon yield from a pyrolyzed carbonmaterial can be about 50%. Accordingly, the ratio of activated carbonproduced per unit mass of polymer processed can be less than about 14,less than about 10, less than about 8, less than about 6, less thanabout 5, less than about 4.5, less than about 4.1. In some embodiments,the ratio of activated carbon produced per unit mass of polymerprocessed is about 4 or lower.

The structure of the polymer precursors is not particularly limited,provided that the polymer precursor is capable of reacting with anotherpolymer precursor or with a second polymer precursor to form a polymer.Polymer precursors include amine-containing compounds,alcohol-containing compounds and carbonyl-containing compounds, forexample in some embodiments the polymer precursors are selected from analcohol, a phenol, a polyalcohol, a sugar, an alkyl amine, an aromaticamine, an aldehyde, a ketone, a carboxylic acid, an ester, a urea, anacid halide and an isocyanate.

In one embodiment, the method comprises use of a first and secondpolymer precursor, and in some embodiments the first or second polymerprecursor is a carbonyl containing compound and the other of the firstor second polymer precursor is an alcohol containing compound. In someembodiments, a first polymer precursor is a phenolic compound and asecond polymer precursor is an aldehyde compound (e.g., formaldehyde).In one embodiment, of the method the phenolic compound is phenol,resorcinol, catechol, hydroquinone, phloroglucinol, or a combinationthereof; and the aldehyde compound is formaldehyde, acetaldehyde,propionaldehyde, butyraldehyde, benzaldehyde, cinnamaldehyde, or acombination thereof. In a further embodiment, the phenolic compound isresorcinol, phenol or a combination thereof, and the aldehyde compoundis formaldehyde. In yet further embodiments, the phenolic compound isresorcinol, and the aldehyde compound is formaldehyde. In someembodiments, the polymer precursors are alcohols and carbonyl compounds(e.g., resorcinol and aldehyde) and they are present in a ratio of about0.5:1.0, respectively.

The polymer precursor materials as disclosed herein include (a)alcohols, phenolic compounds, and other mono- or polyhydroxy compoundsand (b) aldehydes, ketones, and combinations thereof. Representativealcohols in this context include straight chain and branched, saturatedand unsaturated alcohols. Suitable phenolic compounds includepolyhydroxy benzene, such as a dihydroxy or trihydroxy benzene.Representative polyhydroxy benzenes include resorcinol (i.e.,1,3-dihydroxy benzene), catechol, hydroquinone, and phloroglucinol.Other suitable compounds in this regard are bisphenols, for instance,bisphenol A. Mixtures of two or more polyhydroxy benzenes can also beused. Phenol (monohydroxy benzene) can also be used. Representativepolyhydroxy compounds include sugars, such as glucose, sucrose,fructose, chitin and other polyols, such as mannitol. Aldehydes in thiscontext include: straight chain saturated aldeydes such as methanal(formaldehyde), ethanal (acetaldehyde), propanal (propionaldehyde),butanal (butyraldehyde), and the like; straight chain unsaturatedaldehydes such as ethenone and other ketenes, 2-propenal(acrylaldehyde), 2-butenal (crotonaldehyde), 3 butenal, and the like;branched saturated and unsaturated aldehydes; and aromatic-typealdehydes such as benzaldehyde, salicylaldehyde, hydrocinnamaldehyde,and the like. Suitable ketones include: straight chain saturated ketonessuch as propanone and 2 butanone, and the like; straight chainunsaturated ketones such as propenone, 2 butenone, and 3-butenone(methyl vinyl ketone) and the like; branched saturated and unsaturatedketones; and aromatic-type ketones such as methyl benzyl ketone(phenylacetone), ethyl benzyl ketone, and the like. The polymerprecursor materials can also be combinations of the precursors describedabove.

In some embodiments, one polymer precursor is an alcohol-containingspecies and another polymer precursor is a carbonyl-containing species.The relative amounts of alcohol-containing species (e.g., alcohols,phenolic compounds and mono- or poly-hydroxy compounds or combinationsthereof) reacted with the carbonyl containing species (e.g. aldehydes,ketones or combinations thereof) can vary substantially. In someembodiments, the ratio of alcohol-containing species to aldehyde speciesis selected so that the total moles of reactive alcohol groups in thealcohol-containing species is approximately the same as the total molesof reactive carbonyl groups in the aldehyde species. Similarly, theratio of alcohol-containing species to ketone species may be selected sothat the total moles of reactive alcohol groups in the alcoholcontaining species is approximately the same as the total moles ofreactive carbonyl groups in the ketone species. The same general 1:1molar ratio holds true when the carbonyl-containing species comprises acombination of an aldehyde species and a ketone species.

In other embodiments, the polymer precursor is a urea or an aminecontaining compound. For example, in some embodiments the polymerprecursor is urea, melamine, hexamethylenetetramine or combinationthereof. Other embodiments include polymer precursors selected fromisocyanates or other activated carbonyl compounds such as acid halidesand the like.

Some embodiments of the disclosed methods include preparation ofsolvent-free polymer gels (and carbon materials) comprisingelectrochemical modifiers. Such electrochemical modifiers include, butare not limited to nitrogen, silicon, and sulfur. In other embodiments,the electrochemical modifier comprises fluorine, iron, tin, silicon,nickel, aluminum, zinc, or manganese. The electrochemical modifier canbe included in the preparation procedure at any step. For example, insome the electrochemical modifier is admixed with the mixture, thepolymer phase or the continuous phase.

In certain embodiments, the electrochemical modifier is introduced intoan already formed polymer by a solvent-free process. For example, incertain embodiments a polymer gel in particulate form is blended with anitrogen containing compound also in particulate form, and the mixtureblended under a temperature sufficient to achieve molecular mobility,and hence non-covalent and/or covalent incorporation between theelectrochemical modifier and the polymer gel. In certain embodiments,the electrochemical modifier is a nitrogen containing compound, forexample, but not limited to, urea or melamine. In certain embodiments,the mixture of polymer gel particles and nitrogen containing compoundparticles can be held at a temperature at or above the glass transitiontemperature of polymer gel particles, or the nitrogen containingcompound particles, or at a temperature that is at or above the glasstransition temperature of both species of particles. In certainembodiments, the mixture of polymer gel particles and nitrogencontaining compound particles can be held at a temperature at or abovethe melting temperature of polymer gel particles, or the nitrogencontaining compound particles, or at a temperature that is at or abovethe melting temperature of both species of particles.

In certain embodiments, the electrochemical modifier is introduced intoan already formed dried polymer by a solvent-free process. For example,in certain embodiments a dried polymer gel in particulate form isblended with a nitrogen containing compound also in particulate form,and the mixture blended under a temperature sufficient to achievemolecular mobility, and hence non-covalent and/or covalent incorporationbetween the electrochemical modifier and the dried polymer gel. Incertain embodiments, the electrochemical modifier is a nitrogencontaining compound, for example, but not limited to, urea or melamine.In certain embodiments, the mixture of dried polymer gel particles andnitrogen containing compound particles can be held at a temperature ator above the glass transition temperature of dried polymer gelparticles, or the nitrogen containing compound particles, or at atemperature that is at or above the glass transition temperature of bothspecies of particles. In certain embodiments, the mixture of driedpolymer gel particles and nitrogen containing compound particles can beheld at a temperature at or above the melting temperature of driedpolymer gel particles, or the nitrogen containing compound particles, orat a temperature that is at or above the melting temperature of bothspecies of particles.

In some embodiments, the gel polymerization process is performed undercatalytic conditions. Accordingly, in some embodiments, the methodcomprises admixing a catalyst with the solvent-free mixture. In someembodiments, the catalyst is a solid at room temperature and pressure.

In some embodiments, the catalyst is a liquid at room temperature andpressure. In some embodiments, the catalyst is a liquid at roomtemperature and pressure that does not provide dissolution of one ormore of the other polymer precursors.

In some embodiments, the catalyst comprises a basic volatile catalyst.For example, in one embodiment, the basic volatile catalyst comprisesammonium carbonate, ammonium bicarbonate, ammonium acetate, ammoniumhydroxide, or combinations thereof. In a further embodiment, the basicvolatile catalyst is ammonium carbonate. In another further embodiment,the basic volatile catalyst is ammonium acetate.

The molar ratio of catalyst to polymer precursor (e.g., phenoliccompound) may have an effect on the final properties of the polymer gelas well as the final properties of the carbon materials. Thus, in someembodiments such catalysts are used in the range of molar ratios of 5:1to 2000:1 polymer precursor:catalyst. In some embodiments, suchcatalysts can be used in the range of molar ratios of 10:1 to 400:1polymer precursor:catalyst. For example in other embodiments, suchcatalysts can be used in the range of molar ratios of 5:1 to 100:1polymer precursor:catalyst. For example, in some embodiments the molarratio of catalyst to polymer precursor is about 400:1. In otherembodiments the molar ratio of catalyst to polymer precursor is about100:1. In other embodiments the molar ratio of catalyst to polymerprecursor is about 50:1. In other embodiments the molar ratio ofcatalyst to polymer precursor is about 10:1. In certain of the foregoingembodiments, the polymer precursor is a phenolic compound such asresorcinol or phenol.

In the specific embodiment wherein one of the polymer precursors isresorcinol and another polymer precursor is formaldehyde, the resorcinolto catalyst ratio can be varied to obtain the desired properties of theresultant polymer gel and carbon materials. In some embodiments of themethods described herein, the molar ratio of resorcinol to catalyst isfrom about 5:1 to about 2000:1 or the molar ratio of resorcinol tocatalyst is from about 10:1 to about 400:1. In further embodiments, themolar ratio of resorcinol to catalyst is from about 5:1 to about 100:1.In further embodiments, the molar ratio of resorcinol to catalyst isfrom about 25:1 to about 50:1. In further embodiments, the molar ratioof resorcinol to catalyst is from about 100:1 to about 5:1.

In certain embodiments, the precursors employed in the solvent freeprocess comprise a compound comprising phenolic species and a compoundcomprising aldehyde species. In some embodiments, where the precursorsemployed in the solvent free process comprise a compound comprisingphenolic species and a compound comprising aldehyde species, the molratio of phenol groups present to aldehdye group present can be varied,for example from 0.001:1 to 1000:1, for example from 0.01:1 to 100:1,for example from 0.02:1 to 50:1, from 0.05 to 20:1, for example from 0.1to 10:1, for example from 0.2:1 to 5:1, for example from 0.25:1 to 4:1,for example from 0.3:1 to 3:1, for example from, 0.5:1 to 2:1. In someembodiments, the mol ratio of phenol groups present to aldehdye group is0.2:1 to 0.8:1, for example 0.3:1 to 0.7:1, for example from 0.4:1 to0.6:1.

In certain related embodiments, the precursors employed in the solventfree process comprise a compound comprising phenolic species and acompound that degrades under the process conditions to evolve aldehydespecies. In some embodiments, where the precursors employed in thesolvent free process comprise a compound comprising phenolic species anda compound that degrades to yield aldehyde species, the mol ratio ofphenol groups present to aldehdye group evolved can be varied, forexample from 0.001:1 to 1000:1, for example from 0.01:1 to 100:1, forexample from 0.02:1 to 50:1, from 0.05 to 20:1, for example from 0.1 to10:1, for example from 0.2:1 to 5:1, for example from 0.25:1 to 4:1, forexample from 0.3:1 to 3:1, for example from, 0.5:1 to 2:1. In someembodiments, the mol ratio of phenol groups present to aldehdye groupevolved is 0.2:1 to 0.8:1, for example 0.3:1 to 0.7:1, for example from0.4:1 to 0.6:1.

In still other embodiments, the method comprises admixing an acid withthe solvent-free mixture. In certain embodiments, the acid is a solid atroom temperature and pressure. In some embodiments, the acid is a liquidat room temperature and pressure. In some embodiments, the acid is aliquid at room temperature and pressure that does not providedissolution of one or more of the other polymer precursors.

The acid may be selected from any number of acids suitable for thepolymerization process. For example, in some embodiments the acid isacetic acid and in other embodiments the acid is oxalic acid. In furtherembodiments, the acid is mixed with the first or second solvent in aratio of acid to solvent of 99:1, 90:10, 75:25, 50:50, 25:75, 20:80,10:90 or 1:90. In other embodiments, the acid is acetic acid and thefirst or second solvent is water. In other embodiments, acidity isprovided by adding a solid acid.

The total content of acid in the mixture can be varied to alter theproperties of the final product. In some embodiments, the acid ispresent from about 1% to about 50% by weight of mixture. In otherembodiments, the acid is present from about 5% to about 25%. In otherembodiments, the acid is present from about 10% to about 20%, forexample about 10%, about 15% or about 20%.

In certain embodiments, the polymer precursor components are blendedtogether and subsequently held for a time and at a temperaturesufficient to achieve polymerization. One or more of the polymerprecursor components can have particle size less than about 20 mm insize, for example less than 10 mm, for example less than 7 mm, forexample, less than 5 mm, for example less than 2 mm, for example lessthan 1 mm, for example less than 100 microns, for example less than 10microns. In some embodiments, the particle size of one or more of thepolymer precursor components is reduced during the blending process.

The blending of one or more polymer precursor components in the absenceof solvent can be accomplished by methods described in the art, forexample ball milling, jet milling, Fritsch milling, planetary mixing,and other mixing methodologies for mixing or blending solid particleswhile controlling the process conditions (e.g., temperature). The mixingor blending process can be accomplish before, during, and/or after (orcombinations thereof) incubation at the reaction temperature.

Reaction parameters include aging the blended mixture at a temperatureand for a time sufficient for the one or more polymer precursors toreact with each other and form a polymer. In this respect, suitableaging temperature ranges from about room temperature to temperatures ator near the melting point of one or more of the polymer precursors. Insome embodiments, suitable aging temperature ranges from about roomtemperature to temperatures at or near the glass transition temperatureof one or more of the polymer precursors, for example about 10° C. belowthe glass transition temperature of one or more of the polymerprecursors. For example, in some embodiments the solvent free mixture isaged at temperatures from about 20° C. to about 600° C., for exampleabout 20° C. to about 500° C., for example about 20° C. to about 400°C., for example about 20° C. to about 300° C., for example about 20° C.to about 200° C. In certain embodiments, the solvent free mixture isaged at temperatures from about 50 to about 250° C.

The reaction duration is generally sufficient to allow the polymerprecursors to react and form a polymer, for example the mixture may beaged anywhere from 1 hour to 48 hours, or more or less depending on thedesired result. Typical embodiments include aging for a period of timeranging from about 2 hours to about 48 hours, for example in someembodiments aging comprises about 12 hours and in other embodimentsaging comprises about 4-8 hours (e.g., about 6 hours).

In some embodiments, the particle size distribution of the polymerparticles exhibit a polydispersity index (Dv,90−Dv,10)/Dv,50, whereinDv,10, Dv,50 and Dv,90 are the particle size at 10%, 50% and 90%,respectively of the particle size distribution by volume) less than1,000, for example less than 100, for example less than 10, for exampleless than 5, for example less than 3, for example less than 2, forexample less than 1.5, for example less than 1. In some embodiments,introduction of aqueous phase to organic phase can be staged such thattwo or more populations of polymer particle size distribution may beachieved. For example, the final polymer particle distribution achievedmay consist of two or more modes, where the ratio between the highestand lowest node is about 1000 or lower, for example about 100 or lower,for example about 50 or lower, for example about 10 or lower, forexample about 5 or lower, for example about 2 or lower.

2. Pyrolysis and Activation of Polymer Gels

The polymer gels described above, can be further processed to obtaincarbon materials. Such processing includes, for example, pyrolysisand/or activation. Generally, in the pyrolysis process, dried polymergels are weighed and placed in a rotary kiln. The temperature ramp isset at 5° C. per minute, the dwell time and dwell temperature are set;cool down is determined by the natural cooling rate of the furnace. Theentire process is usually run under an inert atmosphere, such as anitrogen environment. Pyrolyzed samples are then removed and weighed.Other pyrolysis processes are well known to those of skill in the art.

In some embodiments, pyrolysis dwell time (the period of time duringwhich the sample is at the desired temperature) is from about 0 minutesto about 120 minutes, from about 20 minutes to about 150 minutes, fromabout 30 minutes to about 100 minutes, from about 50 minutes to about 60minutes or from about 55 minutes to about 60 minutes.

Pyrolysis may also be carried out more slowly than described above. Forexample, in one embodiment the pyrolysis is carried out in about 120 to480 minutes. In other embodiments, the pyrolysis is carried out in about120 to 240 minutes.

In some embodiments, the pyrolysis dwell temperature ranges from about500° C. to 2400° C. In some embodiments, the pyrolysis dwell temperatureranges from about 600° C. to 1800° C. In other embodiments the pyrolysisdwell temperature ranges from about 700° C. to about 1200° C. In otherembodiments the pyrolysis dwell temperature ranges from about 850° C. toabout 1050° C. In other embodiments the pyrolysis dwell temperatureranges from about 800° C. to about 900° C. In some embodiments, thepyrolysis dwell temperature is about 600° C. or 900° C. In some otherspecific embodiments, the pyrolysis dwell temperature ranges from about550° C. to about 900° C.

In some embodiments, the pyrolysis dwell temperature is varied duringthe course of pyrolysis. In one embodiment, the pyrolysis is carried outin a rotary kiln with separate, distinct heating zones. The temperaturefor each zone is sequentially decreased from the entrance to the exitend of the rotary kiln tube. In one embodiment, the pyrolysis is carriedout in a rotary kiln with separate distinct heating zones, and thetemperature for each zone is sequentially increased from entrance toexit end of the rotary kiln tube.

Activation time and activation temperature both have a large impact onthe performance of the resulting activated carbon material, as well asthe manufacturing cost thereof. Increasing the activation temperatureand the activation dwell time results in higher activation percentages,which generally correspond to the removal of more material compared tolower temperatures and shorter dwell times. Activation temperature canalso alter the pore structure of the carbon where lower temperaturesresult in more microporous carbon and higher temperatures result inmesoporosity. This is a result of the activation gas diffusion limitedreaction that occurs at higher temperatures and reaction kinetic drivenreactions that occur at lower temperature. Higher activation percentageoften increases performance of the final activated carbon, but it alsoincreases cost by reducing overall yield. Improving the level ofactivation corresponds to achieving a higher performance product at alower cost.

Pyrolyzed polymer gels may be activated by contacting the pyrolyzedpolymer gel with an activating agent. Many gases are suitable foractivating, for example gases which contain oxygen. Non-limitingexamples of activating gases include carbon dioxide, carbon monoxide,steam, oxygen and combinations thereof. Activating agents may alsoinclude corrosive chemicals such as acids, bases or salts (e.g.,phosphoric acid, acetic acid, citric acid, formic acid, oxalic acid,uric acid, lactic acid, potassium hydroxide, sodium hydroxide, zincchloride, etc.). Other activating agents are known to those skilled inthe art.

In some embodiments, the activation time is between 1 minute and 48hours. In other embodiments, the activation time is between 10 minuteand 24 hours. In other embodiments, the activation time is between 60minutes and 24 hours. In other embodiments, the activation time isbetween 2 hour and 24 hours. In further embodiments, the activation timeis between 12 hours and 24 hours. In certain other embodiments, theactivation time is between 30 min and 8 hours. In some furtherembodiments, the activation time is between 3 hour and 6 hours.

Pyrolyzed polymer gels may be activated using any number of suitableapparatuses known to those skilled in the art, for example, fluidizedbeds, rotary kilns, elevator kilns, roller hearth kilns, pusher kilns,etc. In one embodiment of the activation process, samples are weighedand placed in a rotary kiln, for which the automated gas controlmanifold is set to ramp at a 20° C. per minute rate. Carbon dioxide isintroduced to the kiln environment for a period of time once the properactivation temperature has been reached. After activation has occurred,the carbon dioxide is replaced by nitrogen and the kiln is cooled down.Samples are weighed at the end of the process to assess the level ofactivation. Other activation processes are well known to those of skillin the art. In some of the embodiments disclosed herein, activationtemperatures may range from 800° C. to 1300° C. In another embodiment,activation temperatures may range from 800° C. to 1050° C. In anotherembodiment, activation temperatures may range from about 850° C. toabout 950° C. In another embodiment, the activation temperature is about900° C. In some embodiments, the carbon materials are activated toachieve a specific surface area ranging from 1700 to 1900 m²/g. Oneskilled in the art will recognize that other activation temperatures,either lower or higher, may be employed.

The degree of activation is measured in terms of the mass percent of thepyrolyzed dried polymer gel that is lost during the activation step. Inone embodiment of the methods described herein, activating comprises adegree of activation from 5% to 90%; or a degree of activation from 10%to 80%; in some cases activating comprises a degree of activation from40% to 70%, or a degree of activation from 45% to 65%.

B. Properties of Polymer Gels

One embodiment of the present disclosure provides a polymer gel preparedby any of the methods disclosure herein. The polymer gels produced bythe disclosed methods are unique in many respects. In some embodiments,the method produces polymer gels having monodisperse or nearmonodisperse particle size distributions. As discussed above, theparticle size of the polymer gels (and carbon materials) can becontrolled by a number of process parameters, including the dry blendingapparatus and blending conditions. For example, in some embodiments thepresent disclosure provides a polymer gel having a particle sizedistribution such that (Dv,90−Dv,10)/Dv,50 is less than 3, whereinDv,10, Dv,50 and Dv,90 are the particle size at 10%, 50% and 90%,respectively of the particle size distribution by volume. In someembodiments, (Dv,90−Dv,10)/Dv,50 is less than 2 and in other embodiments(Dv90−Dv10)/Dv50 is less than 1.

The specific surface area of the polymer gels as determined by BETanalysis ranges from about 1 m²/g to about 1000 m²/g. In someembodiments, the specific surface area ranges from about 1 m²/g to about100 m²/g. In other embodiments, the specific surface area ranges fromabout 300 m²/g to about 700 m²/g. In some other embodiments, thespecific surface area ranges from about 300 m²/g to about 400 m²/g. Insome other embodiments, the specific surface area ranges from about 400m²/g to about 500 m²/g. In some other embodiments, the specific surfacearea ranges from about 500 m²/g to about 600 m²/g. In some otherembodiments, the specific surface area ranges from about 600 m²/g toabout 700 m²/g.

The total pore volume of the polymer gels ranges from about 0.01 cc/g toabout 1.5 cc/g. For example, in some embodiments the total pore volumeranges from about 0.1 cc/g to about 0.9 cc/g. In other embodiments thetotal pore volume ranges from about 0.2 cc/g to about 0.8 cc/g. In otherembodiments the total pore volume ranges from about 0.3 cc/g to about0.6 cc/g. In other embodiments the total pore volume ranges from about0.6 cc/g to about 0.9 cc/g.

In other embodiments, the polymer gel comprises a total of less than 500ppm of all other elements having atomic numbers ranging from 11 to 92.For example, in some other embodiments the polymer gel comprises lessthan 200 ppm, less than 100 ppm, less than 50 ppm, less than 25 ppm,less than 10 ppm, less than 5 ppm or less than 1 ppm of all otherelements having atomic numbers ranging from 11 to 92. In someembodiments, the electrochemical modifier content and impurity contentof the polymer gels can be determined by proton induced x-ray emission(PIXE) analysis.

In some embodiments, the polymer gel is a dried polymer gel, forexample, a polymer cryogel. In other embodiments, the dried polymer gelis a polymer xerogel or a polymer aerogel. In some embodiments, thepolymer precursors are selected from aliphatic and aromatic alcohols,aliphatic and aromatic amines and carbonyl-containing compounds. Forexample, the polymer precursors may be selected from an alcohol, aphenol, a polyalcohol, a sugar, an alkyl amine, an aromatic amine, analdehyde, a ketone, a carboxylic acid, an ester, a urea, an acid halideand an isocyanate. In some specific embodiments, the polymer gels areprepared from phenolic compounds and aldehyde compounds, for example, inone embodiment, the polymer gels can be produced from resorcinol andformaldehyde. In some embodiments, acidity can be provided bydissolution of a solid acid compound, by employing an acid as thereaction solvent or by employing a mixed solvent system where one of thesolvents is an acid.

Some embodiments of the disclosed process comprise polymerization toform a polymer gel in the presence of a basic volatile catalyst.Accordingly, in some embodiments, the polymer gel comprises one or moresalts, for example, in some embodiments the one or more salts are basicvolatile salts. Examples of basic volatile salts include, but are notlimited to, ammonium carbonate, ammonium bicarbonate, ammonium acetate,ammonium hydroxide, and combinations thereof. Accordingly, in someembodiments, the present disclosure provides a polymer gel comprisingammonium carbonate, ammonium bicarbonate, ammonium acetate, ammoniumhydroxide, or combinations thereof. In further embodiments, the polymergel comprises ammonium carbonate. In other further embodiments, thepolymer gel comprises ammonium acetate.

The disclosed methods are useful for preparation polymer gels havinghigh purity as determined by PIXE analysis and/or ash content. Asdescribed herein, any intentionally added electrochemical modifier isnot considered an impurity and thus excluded from the specificallydescribed PIXE and ash content values. In some embodiments, the polymergels comprise low ash content which may contribute to the low ashcontent of a carbon material prepared therefrom. Thus, in someembodiments, the ash content of the polymer gel ranges from 0.1% to0.001%. In other embodiments, the ash content of the polymer gel is lessthan 0.1%, less than 0.08%, less than 0.05%, less than 0.03%, less than0.025%, less than 0.01%, less than 0.0075%, less than 0.005% or lessthan 0.001%.

In other embodiments, the polymer gel has a total PIXE impurity contentof less than 500 ppm and an ash content of less than 0.08%. In a furtherembodiment, the polymer gel has a total PIXE impurity content of lessthan 300 ppm and an ash content of less than 0.05%. In another furtherembodiment, the polymer gel has a total PIXE impurity content of lessthan 200 ppm and an ash content of less than 0.02%. In another furtherembodiment, the polymer gel has a total PIXE impurity content of lessthan 200 ppm and an ash content of less than 0.01%.

Polymer gels comprising impurities generally yield carbon materialswhich also comprise impurities, and thus potentially undesiredelectrochemical properties. Accordingly, one aspect of the presentdisclosure is a polymer gel prepared via the disclosed methods andhaving low levels of residual undesired impurities. The amount ofindividual PIXE impurities present in the polymer gel can be determinedby proton induced x-ray emission. In some embodiments, the level ofsodium present in the polymer gel is less than 1000 ppm, less than 500ppm, less than 100 ppm, less than 50 ppm, less than 10 ppm, or less than1 ppm. In some embodiments, the level of magnesium present in thepolymer gel is less than 1000 ppm, less than 100 ppm, less than 50 ppm,less than 10 ppm, or less than 1 ppm. As noted above, in someembodiments other impurities such as hydrogen, oxygen and/or nitrogenmay be present in levels ranging from less than 10% to less than 0.01%.

In some specific embodiments, the polymer gel comprises less than 100ppm sodium, less than 300 ppm silicon, less than 50 ppm sulfur, lessthan 100 ppm calcium, less than 20 ppm iron, less than 10 ppm nickel,less than 40 ppm copper, less than 5 ppm chromium and less than 5 ppmzinc. In other specific embodiments, the polymer gel comprises less than50 ppm sodium, less than 100 ppm silicon, less than 30 ppm sulfur, lessthan 50 ppm calcium, less than 10 ppm iron, less than 5 ppm nickel, lessthan 20 ppm copper, less than 2 ppm chromium and less than 2 ppm zinc.

In other specific embodiments, the polymer gel comprises less than 50ppm sodium, less than 50 ppm silicon, less than 30 ppm sulfur, less than10 ppm calcium, less than 2 ppm iron, less than 1 ppm nickel, less than1 ppm copper, less than 1 ppm chromium and less than 1 ppm zinc.

In some other specific embodiments, the polymer gel comprises less than100 ppm sodium, less than 50 ppm magnesium, less than 50 ppm aluminum,less than 10 ppm sulfur, less than 10 ppm chlorine, less than 10 ppmpotassium, less than 1 ppm chromium and less than 1 ppm manganese.

The disclosed method yields a polymer gel comprising various specificsurface areas depending on the exact reaction parameters. Without beingbound by theory, it is believed that the surface area of the polymer gelcontributes, at least in part, to the surface area properties of thecarbon materials. The surface area can be measured using the BETtechnique well-known to those of skill in the art. In one embodiment ofany of the aspects disclosed herein the polymer gel comprises a BETspecific surface area of at least 0.01 m²/g, at least 1 m²/g, at least10 m²/g, at least 50 m²/g, at least 100 m²/g, at least 250 m²/g, atleast 400 m²/g, at least 500 m²/g, at least 600 m²/g, at least 700 m²/g,at least 800 m²/g, or at least 900 m²/g, or at least 1000 m²/g, or atleast 1100 m²/g.

In one embodiment, the polymer gel comprises a BET specific surface areaof 100 m²/g to 1000 m²/g. Alternatively, the polymer gel comprises a BETspecific surface area of between 150 m²/g and 900 m²/g. Alternatively,the polymer gel comprises a BET specific surface area of between 400m²/g and 800 m²/g.

In one embodiment, the polymer gel comprises a tap density of from 0.10g/cc to 1 g/cc. In another embodiment, the polymer gel comprises a tapdensity of from 0.10 g/cc to 0.6 g/cc. In one embodiment, the polymergel comprises a tap density of from 0.3 g/cc to 0.6 g/cc. In oneembodiment of the present disclosure, the polymer gel comprises a BETspecific surface area of at least 150 m²/g and a tap density of lessthan 0.60 g/cc. Alternately, the polymer gel comprises a BET specificsurface area of at least 250 m²/g and a tap density of less than 0.4g/cc. In another embodiment, the polymer gel comprises a BET specificsurface area of at least 500 m²/g and a tap density of less than 0.30g/cc.

In one embodiment, the polymer gel comprises a fractional pore volume ofpores at or below 500 angstroms that comprises at least 25% of the totalpore volume, 50% of the total pore volume, at least 75% of the totalpore volume, at least 90% of the total pore volume or at least 99% ofthe total pore volume. In another embodiment, the polymer gel comprisesa fractional pore volume of pores at or below 20 nm that comprises atleast 50% of the total pore volume, at least 75% of the total porevolume, at least 90% of the total pore volume or at least 99% of thetotal pore volume.

In some embodiments, the amount of nitrogen adsorbed per mass of polymergel at 0.05 relative pressure is at least 10% of the total nitrogenadsorbed up to 0.99 relative pressure or at least 20% of the totalnitrogen adsorbed up to 0.99 relative pressure. In another embodiment,the amount of nitrogen adsorbed per mass of polymer gel at 0.05 relativepressure is between 10% and 50% of the total nitrogen adsorbed up to0.99 relative pressure, is between 20% and 60% of the total nitrogenadsorbed up to 0.99 relative pressure or is between 20% and 30% of thetotal nitrogen adsorbed up to 0.99 relative pressure.

In one embodiment, the polymer gel comprises a fractional pore surfacearea of pores at or below 100 nm that comprises at least 50% of thetotal pore surface area, at least 75% of the total pore surface area, atleast 90% of the total pore surface area or at least 99% of the totalpore surface area. In another embodiment, the polymer gel comprises afractional pore surface area of pores at or below 20 nm that comprisesat least 50% of the total pore surface area, at least 75% of the totalpore surface area, at least 90% of the total pore surface or at least99% of the total pore surface area.

As described in more detail above, methods for preparing the disclosedcarbon materials may include pyrolysis of a polymer gel. In someembodiments, the pyrolyzed polymer gels have a surface area from about 1to about 1200 m²/g. In other embodiments, the pyrolyzed polymer gelshave a surface area from about 1 to about 100 m²/g. In otherembodiments, the pyrolyzed polymer gels have a surface area from about500 to about 800 m²/g. In other embodiments, the pyrolyzed polymer gelshave a surface area from about 500 to about 700 m²/g.

In other embodiments, the pyrolyzed polymer gels have a tap density fromabout 0.1 to about 1.0 g/cc. In other embodiments, the pyrolyzed polymergels have a tap density from about 0.3 to about 0.6 g/cc. In otherembodiments, the pyrolyzed polymer gels have a tap density from about0.3 to about 0.5 g/cc.

In some embodiments, the polymer gels exhibit a mean particle diameterranging from about 4 μm to about 4 mm. In other embodiments, the meanparticle diameter ranges from about 10 μm to about 1 mm. Yet in otherembodiments, the mean particle diameter ranges from about 20 μm to about500 μm. Still in other embodiments, the mean particle diameter rangesfrom about 500 μm to about 4 mm. Yet still in other embodiments, themean particle diameter ranges from about 2 μm to about 300 μm.

In still other embodiments, the polymer gels comprise a monodisperse, ornear monodisperse particle size distribution. For example, in someembodiments the polymer gels have a particle size distribution such that(Dv,90−Dv,10)/Dv,50 is less than 3, wherein Dv,10, Dv,50 and Dv,90 arethe particle size at 10%, 50% and 90%, respectively of the particle sizedistribution by volume. In further embodiments, (Dv,90−Dv,10)/Dv,50 isless than 2 or even less than 1. In still other embodiments,(Dv,90−Dv,10)/Dv,50 is less than 1,000, less than 100, less than 10,less than 5, less than 3, less than 2, less than 1.5 or even less than1.

Since the polymer gels may comprise electrochemical modifiers, theelemental content of the gels may vary. In some embodiments, the polymergels comprise greater than about 100 ppm of an electrochemical modifier.In certain embodiments, the electrochemical modifier is selected fromnitrogen, iron, tin, silicon, nickel, aluminum and manganese. In someembodiments, the electrochemical modifier is silicon and in otherembodiments the electrochemical modifier is nitrogen.

The amount of electrochemical modifier in the polymer gels is controlledto a level desirable for the final carbon material. Accordingly, in someembodiments, the polymer gel comprises at least 0.10%, at least 0.25%,at least 0.50%, at least 1.0%, at least 5.0%, at least 10%, at least25%, at least 50%, at least 75%, at least 90%, at least 95%, at least99% or at least 99.5% of the electrochemical modifier. For example, insome embodiments, the polymer gels comprise between 0.5% and 99.5%carbon and between 0.5% and 99.5% electrochemical modifier. The percentof the electrochemical modifier is calculated on weight percent basis(wt %).

C. Properties of Carbon Materials

One embodiment of the present disclosure provides a carbon materialprepared by any of the methods disclosed herein. The pore sizedistribution of the carbon materials may contribute to the superiorperformance of electrical devices comprising the carbon materialsrelative to devices comprising other known carbon materials. Forexample, in some embodiments, the carbon material comprises an optimizedblend of both micropores and mesopores and may also comprise low surfacefunctionality upon pyrolysis and/or activation. In other embodiments,the carbon material comprises a total of less than 500 ppm of allelements having atomic numbers ranging from 11 to 92, as measured byproton induced x-ray emission. The high purity and optimized microporeand/or mesopore distribution make the carbon materials ideal for use inelectrical storage and distribution devices, for exampleultracapacitors.

As noted above, activated carbon particles are widely employed as anenergy storage material. In this regard, a critically importantcharacteristic is high power density, which is possible with electrodesthat have low ionic resistance that yield high frequency response. It isimportant to achieve a low ionic resistance, for instance in situationswith device ability to respond to cyclic performance is a constraint.The disclosed methods are useful for preparing carbon material thatsolves the problem of how to optimize an electrode formulation andmaximize the power performance of electrical energy storage anddistribution devices. Devices comprising the carbon materials exhibitlong-term stability, fast response time and high pulse powerperformance.

In some embodiments, the disclosed methods produce carbon materialscomprising micropore and/or mesopore structure, which is typicallydescribed in terms of fraction (percent) of total pore volume residingin either micropores or mesopores or both. Accordingly, in someembodiments the pore structure of the carbon materials comprises from20% to 90% micropores. In other embodiments, the pore structure of thecarbon materials comprises from 30% to 70% micropores. In otherembodiments, the pore structure of the carbon materials comprises from40% to 60% micropores. In other embodiments, the pore structure of thecarbon materials comprises from 40% to 50% micropores. In otherembodiments, the pore structure of the carbon materials comprises from43% to 47% micropores. In certain embodiments, the pore structure of thecarbon materials comprises about 45% micropores.

The mesoporosity of the carbon materials may contribute to high ionmobility and low resistance. In some embodiments, the pore structure ofthe carbon materials comprises from 20% to 80% mesopores. In otherembodiments, the pore structure of the carbon materials comprises from30% to 70% mesopores. In other embodiments, the pore structure of thecarbon materials comprises from 40% to 60% mesopores. In otherembodiments, the pore structure of the carbon materials comprises from50% to 60% mesopores. In other embodiments, the pore structure of thecarbon materials comprises from 53% to 57% mesopores. In otherembodiments, the pore structure of the carbon materials comprises about55% mesopores.

An optimized blend of micropores and mesopores within the carbonmaterials may contribute to the enhanced electrochemical performance ofthe same. Thus, in some embodiments the pore structure of the carbonmaterials comprises from 20% to 80% micropores and from 20% to 80%mesopores. In other embodiments, the pore structure of the carbonmaterials comprises from 30% to 70% micropores and from 30% to 70%mesopores. In other embodiments, the pore structure of the carbonmaterials comprises from 40% to 60% micropores and from 40% to 60%mesopores. In other embodiments, the pore structure of the carbonmaterials comprises from 40% to 50% micropores and from 50% to 60%mesopores. In other embodiments, the pore structure of the carbonmaterials comprises from 43% to 47% micropores and from 53% to 57%mesopores. In other embodiments, the pore structure of the carbonmaterials comprises about 45% micropores and about 55% mesopores.

In other variations, the carbon materials do not have a substantialvolume of pores greater than 20 nm. For example, in certain embodimentsthe carbon materials comprise less than 25%, less than 20%, less than15%, less than 10%, less than 5%, less than 2.5% or even less than 1% ofthe total pore volume in pores greater than 20 nm.

In other variations, the carbon materials do not have a substantialvolume of macropores (i.e., pores greater than 50 nm). For example, incertain embodiments the carbon materials comprise less than 25%, lessthan 20%, less than 15%, less than 10%, less than 5%, less than 2.5%,less than 1%, or even less than 0.1% of the total pore volume inmacropores.

The porosity of the carbon materials contributes to their enhancedelectrochemical performance. Accordingly, in one embodiment the carbonmaterial comprises a pore volume residing in pores less than 20angstroms of at least 1.8 cc/g, at least 1.2, at least 0.6, at least0.30 cc/g, at least 0.25 cc/g, at least 0.20 cc/g or at least 0.15 cc/g.In other embodiments, the carbon material comprises a pore volumeresiding in pores greater than 20 angstroms of at least 7 cc/g, at least5 cc/g, at least 4.00 cc/g, at least 3.75 cc/g, at least 3.50 cc/g, atleast 3.25 cc/g, at least 3.00 cc/g, at least 2.75 cc/g, at least 2.50cc/g, at least 2.25 cc/g, at least 2.00 cc/g, at least 1.90 cc/g, 1.80cc/g, 1.70 cc/g, 1.60 cc/g, 1.50 cc/g, 1.40 cc/g, at least 1.30 cc/g, atleast 1.20 cc/g, at least 1.10 cc/g, at least 1.00 cc/g, at least 0.85cc/g, at least 0.80 cc/g, at least 0.75 cc/g, at least 0.70 cc/g, atleast 0.65 cc/g, at least 0.50 cc/g, at least 0.4 cc/g, at least 0.2cc/g or at least 0.1 cc/g.

In other embodiments, the carbon material comprises a pore volume of atleast 7.00 cc/g, at least 5.00 cc/g, at least 4.00 cc/g, at least 3.75cc/g, at least 3.50 cc/g, at least 3.25 cc/g, at least 3.00 cc/g, atleast 2.75 cc/g, at least 2.50 cc/g, at least 2.25 cc/g, at least 2.00cc/g, at least 1.90 cc/g, 1.80 cc/g, 1.70 cc/g, 1.60 cc/g, 1.50 cc/g, atleast 1.40 cc/g, at least 1.30 cc/g, at least 1.20 cc/g, at least 1.0cc/g, at least 0.8 cc/g, at least 0.6 cc/g, at least 0.4 cc/g, at least0.2 cc/g or at least 0.1 cc/g for pores ranging from 20 angstroms to 500angstroms.

In other embodiments, the carbon material comprises a pore volume of atleast at least 7.00 cc/g, at least 5.00 cc/g, 4.00 cc/g, at least 3.75cc/g, at least 3.50 cc/g, at least 3.25 cc/g, at least 3.00 cc/g, atleast 2.75 cc/g, at least 2.50 cc/g, at least 2.25 cc/g, at least 2.00cc/g, at least 1.90 cc/g, 1.80 cc/g, 1.70 cc/g, 1.60 cc/g, 1.50 cc/g,1.40 cc/g, at least 1.30 cc/g, at least 1.20 cc/g, at least 1.10 cc/g,at least 1.00 cc/g, at least 0.85 cc/g, at least 0.80 cc/g, at least0.75 cc/g, at least 0.70 cc/g, at least 0.65 cc/g, at least 0.50 cc/g,at least 1.40 cc/g, at least 1.30 cc/g, at least 1.20 cc/g, at least 1.0cc/g, at least 0.8 cc/g, at least 0.6 cc/g, at least 0.4 cc/g, at least0.2 cc/g or at least 0.1 cc/g for pores ranging from 20 angstroms to 300angstroms.

In other embodiments, the carbon material comprises a pore volume of atleast 7 cc/g, at least 5 cc/g, at least 4.00 cc/g, at least 3.75 cc/g,at least 3.50 cc/g, at least 3.25 cc/g, at least 3.00 cc/g, at least2.75 cc/g, at least 2.50 cc/g, at least 2.25 cc/g, at least 2.00 cc/g,at least 1.90 cc/g, 1.80 cc/g, 1.70 cc/g, 1.60 cc/g, 1.50 cc/g, 1.40cc/g, at least 1.30 cc/g, at least 1.20 cc/g, at least 1.0 cc/g, atleast 0.8 cc/g, at least 0.6 cc/g, at least 0.4 cc/g, at least 0.2 cc/g,at least 0.1 cc/g for pores ranging from 20 angstroms to 1000 angstroms.

In other embodiments, the carbon material comprises a pore volume of atleast 7 cc/g, at least 5 cc/g, at least 4.00 cc/g, at least 3.75 cc/g,at least 3.50 cc/g, at least 3.25 cc/g, at least 3.00 cc/g, at least2.75 cc/g, at least 2.50 cc/g, at least 2.25 cc/g, at least 2.00 cc/g,at least 1.90 cc/g, 1.80 cc/g, 1.70 cc/g, 1.60 cc/g, 1.50 cc/g, 1.40cc/g, at least 1.30 cc/g, at least 1.20 cc/g, at least 1.0 cc/g, atleast 0.8 cc/g, at least 0.6 cc/g, at least 0.4 cc/g, at least 0.2 cc/g,at least 0.1 cc/g for pores ranging from 20 angstroms to 2000 angstroms.

In other embodiments, the carbon material comprises a pore volume of atleast 7 cc/g, at least 5 cc/g, at least 4.00 cc/g, at least 3.75 cc/g,at least 3.50 cc/g, at least 3.25 cc/g, at least 3.00 cc/g, at least2.75 cc/g, at least 2.50 cc/g, at least 2.25 cc/g, at least 2.00 cc/g,at least 1.90 cc/g, 1.80 cc/g, 1.70 cc/g, 1.60 cc/g, 1.50 cc/g, 1.40cc/g, at least 1.30 cc/g, at least 1.20 cc/g, at least 1.0 cc/g, atleast 0.8 cc/g, at least 0.6 cc/g, at least 0.4 cc/g, at least 0.2 cc/g,at least 0.1 cc/g for pores ranging from 20 angstroms to 5000 angstroms.

In other embodiments, the carbon material comprises a pore volume of atleast 7 cc/g, at least 5 cc/g, at least 4.00 cc/g, at least 3.75 cc/g,at least 3.50 cc/g, at least 3.25 cc/g, at least 3.00 cc/g, at least2.75 cc/g, at least 2.50 cc/g, at least 2.25 cc/g, at least 2.00 cc/g,at least 1.90 cc/g, 1.80 cc/g, 1.70 cc/g, 1.60 cc/g, 1.50 cc/g, 1.40cc/g, at least 1.30 cc/g, at least 1.20 cc/g, at least 1.0 cc/g, atleast 0.8 cc/g, at least 0.6 cc/g, at least 0.4 cc/g, at least 0.2 cc/g,at least 0.1 cc/g for pores ranging from 20 angstroms to 1 micron.

In other embodiments, the carbon material comprises a pore volume of atleast 7 cc/g, at least 5 cc/g, at least 4.00 cc/g, at least 3.75 cc/g,at least 3.50 cc/g, at least 3.25 cc/g, at least 3.00 cc/g, at least2.75 cc/g, at least 2.50 cc/g, at least 2.25 cc/g, at least 2.00 cc/g,at least 1.90 cc/g, 1.80 cc/g, 1.70 cc/g, 1.60 cc/g, 1.50 cc/g, 1.40cc/g, at least 1.30 cc/g, at least 1.20 cc/g, at least 1.0 cc/g, atleast 0.8 cc/g, at least 0.6 cc/g, at least 0.4 cc/g, at least 0.2 cc/g,at least 0.1 cc/g for pores ranging from 20 angstroms to 2 microns.

In other embodiments, the carbon material comprises a pore volume of atleast 7 cc/g, at least 5 cc/g, at least 4.00 cc/g, at least 3.75 cc/g,at least 3.50 cc/g, at least 3.25 cc/g, at least 3.00 cc/g, at least2.75 cc/g, at least 2.50 cc/g, at least 2.25 cc/g, at least 2.00 cc/g,at least 1.90 cc/g, 1.80 cc/g, 1.70 cc/g, 1.60 cc/g, 1.50 cc/g, 1.40cc/g, at least 1.30 cc/g, at least 1.20 cc/g, at least 1.0 cc/g, atleast 0.8 cc/g, at least 0.6 cc/g, at least 0.4 cc/g, at least 0.2 cc/g,at least 0.1 cc/g for pores ranging from 20 angstroms to 3 microns.

In other embodiments, the carbon material comprises a pore volume of atleast 7 cc/g, at least 5 cc/g, at least 4.00 cc/g, at least 3.75 cc/g,at least 3.50 cc/g, at least 3.25 cc/g, at least 3.00 cc/g, at least2.75 cc/g, at least 2.50 cc/g, at least 2.25 cc/g, at least 2.00 cc/g,at least 1.90 cc/g, 1.80 cc/g, 1.70 cc/g, 1.60 cc/g, 1.50 cc/g, 1.40cc/g, at least 1.30 cc/g, at least 1.20 cc/g, at least 1.0 cc/g, atleast 0.8 cc/g, at least 0.6 cc/g, at least 0.4 cc/g, at least 0.2 cc/g,at least 0.1 cc/g for pores ranging from 20 angstroms to 4 microns.

In other embodiments, the carbon material comprises a pore volume of atleast 7 cc/g, at least 5 cc/g, at least 4.00 cc/g, at least 3.75 cc/g,at least 3.50 cc/g, at least 3.25 cc/g, at least 3.00 cc/g, at least2.75 cc/g, at least 2.50 cc/g, at least 2.25 cc/g, at least 2.00 cc/g,at least 1.90 cc/g, 1.80 cc/g, 1.70 cc/g, 1.60 cc/g, 1.50 cc/g, 1.40cc/g, at least 1.30 cc/g, at least 1.20 cc/g, at least 1.0 cc/g, atleast 0.8 cc/g, at least 0.6 cc/g, at least 0.4 cc/g, at least 0.2 cc/g,at least 0.1 cc/g for pores ranging from 20 angstroms to 5 microns.

In yet other embodiments, the carbon materials comprise a total porevolume of at least 4.00 cc/g, at least 3.75 cc/g, at least 3.50 cc/g, atleast 3.25 cc/g, at least 3.00 cc/g, at least 2.75 cc/g, at least 2.50cc/g, at least 2.25 cc/g, at least 2.00 cc/g, at least 1.90 cc/g, 1.80cc/g, 1.70 cc/g, 1.60 cc/g, 1.50 cc/g, 1.40 cc/g, at least 1.30 cc/g, atleast 1.20 cc/g, at least 1.10 cc/g, at least 1.00 cc/g, at least 0.85cc/g, at least 0.80 cc/g, at least 0.75 cc/g, at least 0.70 cc/g, atleast 0.65 cc/g, at least 0.60 cc/g, at least 0.55 cc/g, at least 0.50cc/g, at least 0.45 cc/g, at least 0.40 cc/g, at least 0.35 cc/g, atleast 0.30 cc/g, at least 0.25 cc/g, at least 0.20 cc/g or at least 0.10cc/g.

In yet other embodiments, the carbon materials comprise a pore volumeresiding in pores of less than 20 angstroms of at least 0.2 cc/g and apore volume residing in pores of between 20 and 300 angstroms of atleast 0.8 cc/g. In yet other embodiments, the carbon materials comprisea pore volume residing in pores of less than 20 angstroms of at least0.5 cc/g and a pore volume residing in pores of between 20 and 300angstroms of at least 0.5 cc/g. In yet other embodiments, the carbonmaterials comprise a pore volume residing in pores of less than 20angstroms of at least 0.6 cc/g and a pore volume residing in pores ofbetween 20 and 300 angstroms of at least 2.4 cc/g. In yet otherembodiments, the carbon materials comprise a pore volume residing inpores of less than 20 angstroms of at least 1.5 cc/g and a pore volumeresiding in pores of between 20 and 300 angstroms of at least 1.5 cc/g.

In some embodiments, the pores of the carbon material comprise a peakpore volume ranging from 2 nm to 10 nm. In other embodiments, the peakpore volume ranges from 10 nm to 20 nm. Yet in other embodiments, thepeak pore volume ranges from 20 nm to 30 nm. Still in other embodiments,the peak pore volume ranges from 30 nm to 40 nm. Yet still in otherembodiments, the peak pore volume ranges from 40 nm to 50 nm. In otherembodiments, the peak pore volume ranges from 50 nm to 100 nm.

In certain embodiments a mesoporous carbon material having low porevolume in the micropore region (e.g., less than 60%, less than 50%, lessthan 40%, less than 30%, less than 20% microporosity) is prepared by thedisclosed methods. For example, the mesoporous carbon can be a polymergel that has been pyrolyzed, but not activated. In some embodiments, thepyrolyzed mesoporous carbon comprises a specific surface area of atleast 400 m²/g, at least 500 m²/g, at least 600 m²/g, at least 675 m²/gor at least 750 m²/g. In other embodiments, the mesoporous carbonmaterial comprises a total pore volume of at least 0.50 cc/g, at least0.60 cc/g, at least 0.70 cc/g, at least 0.80 cc/g or at least 0.90 cc/g.In yet other embodiments, the mesoporous carbon material comprises a tapdensity of at least 0.30 g/cc, at least 0.35 g/cc, at least 0.40 g/cc,at least 0.45 g/cc, at least 0.50 g/cc or at least 0.55 g/cc.

In other embodiments, the carbon materials comprise a total pore volumeranging greater than or equal to 0.1 cc/g, and in other embodiments thecarbon materials comprise a total pore volume less than or equal to 0.6cc/g. In other embodiments, the carbon materials comprise a total porevolume ranging from about 0.1 cc/g to about 0.6 cc/g. In some otherembodiments, the total pore volume of the carbon materials ranges fromabout 0.1 cc/g to about 0.2 cc/g. In some other embodiments, the totalpore volume of the carbon materials ranges from about 0.2 cc/g to about0.3 cc/g. In some other embodiments, the total pore volume of the carbonmaterials ranges from about 0.3 cc/g to about 0.4 cc/g. In some otherembodiments, the total pore volume of the carbon materials ranges fromabout 0.4 cc/g to about 0.5 cc/g. In some other embodiments, the totalpore volume of the carbon materials ranges from about 0.5 cc/g to about0.6 cc/g.

The carbon material comprises low total PIXE impurities. Thus, in someembodiments the total PIXE impurity content of all other PIXE elementsin the carbon material (as measured by proton induced x-ray emission) isless than 1000 ppm. In other embodiments, the total PIXE impuritycontent of all other PIXE elements in the carbon material is less than800 ppm, less than 500 ppm, less than 300 ppm, less than 200 ppm, lessthan 150 ppm, less than 100 ppm, less than 50 ppm, less than 25 ppm,less than 10 ppm, less than 5 ppm or less than 1 ppm. In furtherembodiments of the foregoing, the carbon material is a pyrolyzed driedpolymer gel, a pyrolyzed polymer cryogel, a pyrolyzed polymer xerogel, apyrolyzed polymer aerogel, an activated dried polymer gel, an activatedpolymer cryogel, an activated polymer xerogel or an activated polymeraerogel.

In addition to low content of undesired PIXE impurities, the disclosedcarbon materials may comprise high total carbon content. In addition tocarbon, the carbon material may also comprise oxygen, hydrogen, nitrogenand the electrochemical modifier. In some embodiments, the materialcomprises at least 75% carbon, 80% carbon, 85% carbon, at least 90%carbon, at least 95% carbon, at least 96% carbon, at least 97% carbon,at least 98% carbon or at least 99% carbon on a weight/weight basis. Insome other embodiments, the carbon material comprises less than 10%oxygen, less than 5% oxygen, less than 3.0% oxygen, less than 2.5%oxygen, less than 1% oxygen or less than 0.5% oxygen on a weight/weightbasis. In other embodiments, the carbon material comprises less than 10%hydrogen, less than 5% hydrogen, less than 2.5% hydrogen, less than 1%hydrogen, less than 0.5% hydrogen or less than 0.1% hydrogen on aweight/weight basis. In other embodiments, the carbon material comprisesless than 5% nitrogen, less than 2.5% nitrogen, less than 1% nitrogen,less than 0.5% nitrogen, less than 0.25% nitrogen or less than 0.01%nitrogen on a weight/weight basis. The oxygen, hydrogen and nitrogencontent of the disclosed carbon materials can be determined bycombustion analysis. Techniques for determining elemental composition bycombustion analysis are well known in the art.

In other embodiments, the carbon content is greater than 98 wt. % asmeasured by CHNO analysis. In another embodiment, the carbon contentranges from 50 to 98 wt. % of the total mass. In yet other embodiments,the carbon content ranges 90 to 98 wt. % of the total mass. In yet otherembodiments, the carbon content ranges from 80 to 90 wt. % of the totalmass. In yet other embodiments, the carbon content ranges from 70 to 80wt. % of the total mass. In yet other embodiments, the carbon contentranges from 60 to 70 wt. % of the total mass.

In another embodiment, the nitrogen content ranges from 0 to 30 wt. % asmeasured by CHNO analysis. In another embodiment, the nitrogen contentranges from 1 to 10 wt %, for example from 5 to 10 wt % of the totalmass. In yet other embodiments, the nitrogen content ranges from 10 to20 wt. % of the total mass. In yet other embodiments, the nitrogencontent ranges from 20 to 30 wt. % of the total mass. In anotherembodiment, the nitrogen content is greater than 30 wt. %.

The carbon and nitrogen content may also be measured as a ratio of C:N.In one embodiment, the C:N ratio ranges from 1:0.001 to 1:1. In anotherembodiment, the C:N ratio ranges from 1:0.001 to 0.01. In yet anotherembodiment, the C:N ratio ranges from 1:0.01 to 1:1. In yet anotherembodiment, the content of nitrogen exceeds the content of carbon.

The carbon materials may also comprise an electrochemical modifier(i.e., a dopant) selected to optimize the electrochemical performance ofthe carbon materials. The electrochemical modifier may be added duringthe polymerization step as described above. For example, theelectrochemical modifier may added to the above described mixture,continuous phase or polymer phase, or included within the polymerizationprocess in any other manner.

The electrochemical modifier may be incorporated within the porestructure and/or on the surface of the carbon material or incorporatedin any number of other ways. For example, in some embodiments, thecarbon materials comprise a coating of the electrochemical modifier(e.g., Al₂O₃) on the surface of the carbon materials. In someembodiments, the carbon materials comprise greater than about 100 ppm ofan electrochemical modifier. In certain embodiments, the electrochemicalmodifier is selected from iron, tin, silicon, nickel, aluminum andmanganese. In some embodiments, the electrochemical modifier is siliconand in other embodiments the electrochemical modifier is nitrogen.

In certain embodiments the electrochemical modifier comprises an elementwith the ability to lithiate from 3 to 0 V versus lithium metal (e.g.silicon, tin, sulfur). In other embodiments, the electrochemicalmodifier comprises metal oxides with the ability to lithiate from 3 to 0V versus lithium metal (e.g. iron oxide, molybdenum oxide, titaniumoxide). In still other embodiments, the electrochemical modifiercomprises elements which do not lithiate from 3 to 0 V versus lithiummetal (e.g. aluminum, manganese, nickel, metal-phosphates). In yet otherembodiments, the electrochemical modifier comprises a non-metal element(e.g. fluorine, nitrogen, hydrogen). In still other embodiments, theelectrochemical modifier comprises any of the foregoing electrochemicalmodifiers or any combination thereof (e.g. tin-silicon, nickel-titaniumoxide).

The electrochemical modifier may be provided in any number of forms. Forexample, in some embodiments the electrochemical modifier comprises asalt. In other embodiments, the electrochemical modifier comprises oneor more elements in elemental form, for example elemental iron, tin,silicon, nickel or manganese. In other embodiments, the electrochemicalmodifier comprises one or more elements in oxidized form, for exampleiron oxides, tin oxides, silicon oxides, nickel oxides, aluminum oxidesor manganese oxides.

In other embodiments, the electrochemical modifier comprises iron. Inother embodiments, the electrochemical modifier comprises tin. In otherembodiments, the electrochemical modifier comprises silicon. In someother embodiments, the electrochemical modifier comprises nickel. In yetother embodiments, the electrochemical modifier comprises aluminum. Inyet other embodiments, the electrochemical modifier comprises manganese.In yet other embodiments, the electrochemical modifier comprises Al₂O₃.

The electrochemical properties of the carbon materials can be modified,at least in part, by the amount of the electrochemical modifier in thecarbon material. Accordingly, in some embodiments, the carbon materialcomprises at least 0.10%, at least 0.25%, at least 0.50%, at least 1.0%,at least 5.0%, at least 10%, at least 25%, at least 50%, at least 75%,at least 90%, at least 95%, at least 99% or at least 99.5% of theelectrochemical modifier. For example, in some embodiments, the carbonmaterials comprise between 0.5% and 99.5% carbon and between 0.5% and99.5% electrochemical modifier. The percent of the electrochemicalmodifier is calculated on weight percent basis (wt %). In some othermore specific embodiments, the electrochemical modifier is selected fromiron, tin, silicon, nickel and manganese.

The total ash content of the carbon material may, in some instances,have an effect on the electrochemical performance of the carbonmaterial. Accordingly, in some embodiments, the ash content of thecarbon material ranges from 0.1% to 0.001% weight percent ash, forexample in some specific embodiments the ash content of the carbonmaterial is less than 0.1%, less than 0.08%, less than 0.05%, less than0.03%, than 0.025%, less than 0.01%, less than 0.0075%, less than 0.005%or less than 0.001%.

In other embodiments, the carbon material comprises a total PIXEimpurity content of less than 500 ppm and an ash content of less than0.08%. In further embodiments, the carbon material comprises a totalPIXE impurity content of less than 300 ppm and an ash content of lessthan 0.05%. In other further embodiments, the carbon material comprisesa total PIXE impurity content of less than 200 ppm and an ash content ofless than 0.05%. In other further embodiments, the carbon materialcomprises a total PIXE impurity content of less than 200 ppm and an ashcontent of less than 0.025%. In other further embodiments, the carbonmaterial comprises a total PIXE impurity content of less than 100 ppmand an ash content of less than 0.02%. In other further embodiments, thecarbon material comprises a total PIXE impurity content of less than 50ppm and an ash content of less than 0.01%.

The amount of individual PIXE impurities present in the disclosed carbonmaterials can be determined by proton induced x-ray emission. IndividualPIXE impurities may contribute in different ways to the overallelectrochemical performance of the disclosed carbon materials. Thus, insome embodiments, the level of sodium present in the carbon material isless than 1000 ppm, less than 500 ppm, less than 100 ppm, less than 50ppm, less than 10 ppm, or less than 1 ppm. As noted above, in someembodiments other impurities such as hydrogen, oxygen and/or nitrogenmay be present in levels ranging from less than 10% to less than 0.01%.

In some embodiments, the carbon material comprises undesired PIXEimpurities near or below the detection limit of the proton induced x-rayemission analysis. For example, in some embodiments the carbon materialcomprises less than 50 ppm sodium, less than 15 ppm magnesium, less than10 ppm aluminum, less than 8 ppm silicon, less than 4 ppm phosphorous,less than 3 ppm sulfur, less than 3 ppm chlorine, less than 2 ppmpotassium, less than 3 ppm calcium, less than 2 ppm scandium, less than1 ppm titanium, less than 1 ppm vanadium, less than 0.5 ppm chromium,less than 0.5 ppm manganese, less than 0.5 ppm iron, less than 0.25 ppmcobalt, less than 0.25 ppm nickel, less than 0.25 ppm copper, less than0.5 ppm zinc, less than 0.5 ppm gallium, less than 0.5 ppm germanium,less than 0.5 ppm arsenic, less than 0.5 ppm selenium, less than 1 ppmbromine, less than 1 ppm rubidium, less than 1.5 ppm strontium, lessthan 2 ppm yttrium, less than 3 ppm zirconium, less than 2 ppm niobium,less than 4 ppm molybdenum, less than 4 ppm, technetium, less than 7 ppmrubidium, less than 6 ppm rhodium, less than 6 ppm palladium, less than9 ppm silver, less than 6 ppm cadmium, less than 6 ppm indium, less than5 ppm tin, less than 6 ppm antimony, less than 6 ppm tellurium, lessthan 5 ppm iodine, less than 4 ppm cesium, less than 4 ppm barium, lessthan 3 ppm lanthanum, less than 3 ppm cerium, less than 2 ppmpraseodymium, less than 2 ppm, neodymium, less than 1.5 ppm promethium,less than 1 ppm samarium, less than 1 ppm europium, less than 1 ppmgadolinium, less than 1 ppm terbium, less than 1 ppm dysprosium, lessthan 1 ppm holmium, less than 1 ppm erbium, less than 1 ppm thulium,less than 1 ppm ytterbium, less than 1 ppm lutetium, less than 1 ppmhafnium, less than 1 ppm tantalum, less than 1 ppm tungsten, less than1.5 ppm rhenium, less than 1 ppm osmium, less than 1 ppm iridium, lessthan 1 ppm platinum, less than 1 ppm silver, less than 1 ppm mercury,less than 1 ppm thallium, less than 1 ppm lead, less than 1.5 ppmbismuth, less than 2 ppm thorium, or less than 4 ppm uranium.

In some specific embodiments, the carbon material comprises less than100 ppm sodium, less than 300 ppm silicon, less than 50 ppm sulfur, lessthan 100 ppm calcium, less than 20 ppm iron, less than 10 ppm nickel,less than 140 ppm copper, less than 5 ppm chromium and less than 5 ppmzinc as measured by proton induced x-ray emission. In other specificembodiments, the carbon material comprises less than 50 ppm sodium, lessthan 30 ppm sulfur, less than 100 ppm silicon, less than 50 ppm calcium,less than 10 ppm iron, less than 5 ppm nickel, less than 20 ppm copper,less than 2 ppm chromium and less than 2 ppm zinc.

In other specific embodiments, the carbon material comprises less than50 ppm sodium, less than 50 ppm silicon, less than 30 ppm sulfur, lessthan 10 ppm calcium, less than 2 ppm iron, less than 1 ppm nickel, lessthan 1 ppm copper, less than 1 ppm chromium and less than 1 ppm zinc.

In some other specific embodiments, the carbon material comprises lessthan 100 ppm sodium, less than 50 ppm magnesium, less than 50 ppmaluminum, less than 10 ppm sulfur, less than 10 ppm chlorine, less than10 ppm potassium, less than 1 ppm chromium and less than 1 ppmmanganese.

The disclosed carbon materials may also comprise a high surface area.While not wishing to be bound by theory, it is thought that the highsurface area may contribute, at least in part, to their superiorelectrochemical performance. Accordingly, in some embodiments, thecarbon material comprises a BET specific surface area of at least 100m²/g, at least 300 m²/g, at least 500 m²/g, at least 1000 m²/g, at least1500 m²/g, at least 2000 m²/g, at least 2400 m²/g, at least 2500 m²/g,at least 2750 m²/g or at least 3000 m²/g. In other embodiments, the BETspecific surface area ranges from about 100 m²/g to about 3000 m²/g, forexample from about 500 m²/g to about 1000 m²/g, from about 1000 m²/g toabout 1500 m²/g, from about 1500 m²/g to about 2000 m²/g, from about2000 m²/g to about 2500 m²/g or from about 2500 m²/g to about 3000 m²/g.For example, in some embodiments of the foregoing, the carbon materialis activated.

In some specific embodiments the surface area ranges from about 50 m²/gto about 1200 m²/g for example from about 50 m²/g to about 400 m²/g. Inother particular embodiments, the surface area ranges from about 200m²/g to about 300 m²/g for example the surface area may be about 250m²/g.

In another embodiment, the carbon material comprises a tap densitybetween 0.1 and 1.0 g/cc, between 0.2 and 0.8 g/cc, between 0.3 and 0.5g/cc or between 0.4 and 0.5 g/cc. In another embodiment, the carbonmaterial has a total pore volume of at least 0.1 cm³/g, at least 0.2cm³/g, at least 0.3 cm³/g, at least 0.4 cm3/g, at least 0.5 cm³/g, atleast 0.7 cm³/g, at least 0.75 cm³/g, at least 0.9 cm³/g, at least 1.0cm³/g, at least 1.1 cm³/g, at least 1.2 cm³/g, at least 1.3 cm³/g, atleast 1.4 cm³/g, at least 1.5 cm³/g or at least 1.6 cm³/g.

The pore size distribution of the disclosed carbon materials is oneparameter that may have an effect on the electrochemical performance ofthe carbon materials. For example, the carbon materials may comprisemesopores with a short effective length (i.e., less than 10 nm, lessthan 5, nm or less than 3 nm as measured by TEM) which decreases iondiffusion distance and may be useful to enhance ion transport andmaximize power. Accordingly, in one embodiment, the carbon materialcomprises a fractional pore volume of pores at or below 100 nm thatcomprises at least 50% of the total pore volume, at least 75% of thetotal pore volume, at least 90% of the total pore volume or at least 99%of the total pore volume. In other embodiments, the carbon materialcomprises a fractional pore volume of pores at or below 20 nm thatcomprises at least 50% of the total pore volume, at least 75% of thetotal pore volume, at least 90% of the total pore volume or at least 99%of the total pore volume.

In another embodiment, the carbon material comprises a fractional poresurface area of pores between 20 and 300 angstroms that comprises atleast 40% of the total pore surface area, at least 50% of the total poresurface area, at least 70% of the total pore surface area or at least80% of the total pore surface area. In another embodiment, the carbonmaterial comprises a fractional pore surface area of pores at or below20 nm that comprises at least 20% of the total pore surface area, atleast 30% of the total pore surface area, at least 40% of the total poresurface area or at least 50% of the total pore surface area.

In another embodiment, the carbon material comprises a fractional poresurface area of pores at or below 100 nm that comprises at least 50% ofthe total pore surface area, at least 75% of the total pore surfacearea, at least 90% of the total pore surface area or at least 99% of thetotal pore surface area. In another embodiment, the carbon materialcomprises a fractional pore surface area of pores at or below 20 nm thatcomprises at least 50% of the total pore surface area, at least 75% ofthe total pore surface area, at least 90% of the total pore surface areaor at least 99% of the total pore surface area.

In another embodiment, the carbon material comprises pores predominantlyin the range of 1000 angstroms or lower, for example 100 angstroms orlower, for example 50 angstroms or lower. Alternatively, the carbonmaterial comprises micropores in the range of 0-20 angstroms andmesopores in the range of 20-300 angstroms. The ratio of pore volume orpore surface in the micropore range compared to the mesopore range canbe in the range of 95:5 to 5:95. Alternatively, the ratio of pore volumeor pore surface in the micropore range compared to the mesopore rangecan be in the range of 20:80 to 60:40.

In other embodiments, the carbon materials are mesoporous and comprisemonodisperse mesopores. As used herein, the term “monodisperse” whenused in reference to a pore size refers generally to a span (furtherdefined as (Dv,90−Dv,10)/Dv, 50 where Dv,10, Dv,50 and Dv,90 refer tothe pore size at 10%, 50% and 90% of the distribution by volume of about3 or less, typically about 2 or less, often about 1.5 or less.

Yet in other embodiments, the carbons materials comprise a pore volumeof at least 1 cc/g, at least 2 cc/g, at least 3 cc/g, at least 4 cc/g orat least 7 cc/g. In one particular embodiment, the carbon materialscomprise a pore volume of from 1 cc/g to 7 cc/g.

In other embodiments, the carbon materials comprise at least 50% of thetotal pore volume residing in pores with a diameter ranging from 50 Å to5000 Å. In some instances, the carbon materials comprise at least 50% ofthe total pore volume residing in pores with a diameter ranging from 50Å to 500 Å. Still in other instances, the carbon materials comprise atleast 50% of the total pore volume residing in pores with a diameterranging from 500 Å to 1000 Å. Yet in other instances, the carbonmaterials comprise at least 50% of the total pore volume residing inpores with a diameter ranging from 1000 Å to 5000 Å.

In some embodiments, the mean particle diameter for the carbon materialsranges from 1 to 1000 microns. In other embodiments the mean particlediameter for the carbon materials ranges from 1 to 100 microns. Still inother embodiments the mean particle diameter for the carbon materialsranges from 1 to 50 microns. Yet in other embodiments, the mean particlediameter for the carbon materials ranges from 5 to 15 microns or from 1to 5 microns. Still in other embodiments, the mean particle diameter forthe carbon materials is about 10 microns. Still in other embodiments,the mean particle diameter for the carbon materials is less than 4, isless than 3, is less than 2, is less than 1 microns.

In some embodiments, the carbon materials exhibit a mean particlediameter ranging from 1 nm to 10 nm. In other embodiments, the meanparticle diameter ranges from 10 nm to 20 nm. Yet in other embodiments,the mean particle diameter ranges from 20 nm to 30 nm. Still in otherembodiments, the mean particle diameter ranges from 30 nm to 40 nm. Yetstill in other embodiments, the mean particle diameter ranges from 40 nmto 50 nm. In other embodiments, the mean particle diameter ranges from50 nm to 100 nm.

In some embodiments, the mean particle diameter for the carbons rangesfrom 1 to 1000 microns. In other embodiments the mean particle diameterfor the carbon ranges from 1 to 100 microns. Still in other embodimentsthe mean particle diameter for the carbon ranges from 5 to 50 microns.Yet in other embodiments, the mean particle diameter for the carbonranges from 5 to 15 microns. Still in other embodiments, the meanparticle diameter for the carbon is about 10 microns.

In some embodiments, the carbon materials exhibit a mean particlediameter ranging from 1 micron to 5 microns. In other embodiments, themean particle diameter ranges from 5 microns to 10 microns. In yet otherembodiments, the mean particle diameter ranges from 10 nm to 20 microns.Still in other embodiments, the mean particle diameter ranges from 20 nmto 30 microns. Yet still in other embodiments, the mean particlediameter ranges from 30 microns to 40 microns. Yet still in otherembodiments, the mean particle diameter ranges from 40 microns to 50microns. In other embodiments, the mean particle diameter ranges from 50microns to 100 microns. In other embodiments, the mean particle diameterranges in the submicron range <1 micron.

In still other embodiments, the carbon materials comprise amonodisperse, or near monodisperse particle size distribution. Forexample, in some embodiments the carbon material has a particle sizedistribution such that (Dv,90−Dv,10)/Dv,50 is less than 3, whereinDv,10, Dv,50 and Dv,90 are the particle size at 10%, 50% and 90%,respectively of the particle size distribution by volume. In furtherembodiments, (Dv,90−Dv,10)/Dv,50 is less than 2 or even less than 1. Instill other embodiments, (Dv,90−Dv,10)/Dv,50 is less than 1,000, lessthan 100, less than 10, less than 5, less than 3, less than 2, less than1.5 or even less than 1.

In yet other embodiments, the carbon materials comprise carbon particleshaving a substantially spherical geometry. Such geometry may improve theperformance of any number of electrical devices comprising the carbonmaterials since the geometry is known to affect particle packing (andthus energy density). In some embodiments, carbon material comprises aplurality of carbon particles, wherein greater than 90% of the carbonparticles have a spherical geometry. For example, in some embodiments,greater than 95% of the carbon particles have a spherical geometry.

D. Characterization of Polymer Gels and Carbon Materials

The structural properties of the final carbon material and intermediatepolymer gels may be measured using Nitrogen sorption at 77K, a methodknown to those of skill in the art. The final performance andcharacteristics of the finished carbon material is important, but theintermediate products (both dried polymer gel and pyrolyzed, but notactivated, polymer gel), can also be evaluated, particularly from aquality control standpoint, as known to those of skill in the art. TheMicromeretics ASAP 2020 is used to perform detailed micropore andmesopore analysis, which reveals a pore size distribution from 0.35 nmto 50 nm in some embodiments. The system produces a nitrogen isothermstarting at a pressure of 10⁻⁷ atm, which enables high resolution poresize distributions in the sub 1 nm range. The software generated reportsutilize a Density Functional Theory (DFT) method to calculate propertiessuch as pore size distributions, surface area distributions, totalsurface area, total pore volume, and pore volume within certain poresize ranges.

The impurity content of the carbon materials can be determined by anynumber of analytical techniques known to those of skill in the art. Oneparticular analytical method useful within the context of the presentdisclosure is proton induced x-ray emission (PIXE). This technique iscapable of measuring the concentration of elements having atomic numbersranging from 11 to 92 at low ppm levels. Accordingly, in one embodimentthe concentration of impurities present in the carbon materials isdetermined by PIXE analysis.

E. Devices Comprising the Carbon Materials

The disclosed carbon materials can be used as electrode material in anynumber of electrical energy storage and distribution devices. Usefuldevices in this regard include, but are not limited to, the devicesdescribed below and in co-pending U.S. application Ser. Nos. 12/748,219;12/897,969; 12/829,282; 13/046,572; 12/965,709; 13/336,975; and61/585,611, each of which are hereby incorporated by reference in theirentireties.

1. EDLCs

The disclosed carbon materials can be used as electrode material in anynumber of electrical energy storage and distribution devices. One suchdevice is an ultracapacitor. Ultracapacitors comprising carbon materialsare described in detail in co-owned U.S. Pat. No. 7,835,136 which ishereby incorporated in its entirety.

EDLCs use electrodes immersed in an electrolyte solution as their energystorage element. Typically, a porous separator immersed in andimpregnated with the electrolyte ensures that the electrodes do not comein contact with each other, preventing electronic current flow directlybetween the electrodes. At the same time, the porous separator allowsionic currents to flow through the electrolyte between the electrodes inboth directions thus forming double layers of charges at the interfacesbetween the electrodes and the electrolyte.

When electric potential is applied between a pair of electrodes of anEDLC, ions that exist within the electrolyte are attracted to thesurfaces of the oppositely-charged electrodes, and migrate towards theelectrodes. A layer of oppositely-charged ions is thus created andmaintained near each electrode surface. Electrical energy is stored inthe charge separation layers between these ionic layers and the chargelayers of the corresponding electrode surfaces. In fact, the chargeseparation layers behave essentially as electrostatic capacitors.Electrostatic energy can also be stored in the EDLCS through orientationand alignment of molecules of the electrolytic solution under influenceof the electric field induced by the potential. This mode of energystorage, however, is secondary.

EDLCS comprising the disclosed carbon material can be employed invarious electronic devices where high power is desired. Accordingly, inone embodiment an electrode comprising the carbon materials is provided.In another embodiment, the electrode comprises activated carbonmaterial. In a further embodiment, an ultracapacitor comprising anelectrode comprising the carbon materials is provided. In a furtherembodiment of the foregoing, the ultrapure synthetic carbon materialcomprises an optimized balance of micropores and mesopores and describedabove.

The disclosed carbon materials find utility in any number of electronicdevices, for example wireless consumer and commercial devices such asdigital still cameras, notebook PCs, medical devices, location trackingdevices, automotive devices, compact flash devices, mobiles phones,PCMCIA cards, handheld devices, and digital music players.Ultracapacitors are also employed in heavy equipment such as: excavatorsand other earth moving equipment, forklifts, garbage trucks, cranes forports and construction and transportation systems such as buses,automobiles and trains.

In one embodiment, the present disclosure is directed to a devicecomprising the carbon materials described herein, wherein the device isan electric double layer capacitor (EDLC) device comprising:

a) a positive electrode and a negative electrode wherein each of thepositive and the negative electrodes comprise the carbon material;

b) an inert porous separator; and

c) an electrolyte;

wherein the positive electrode and the negative electrode are separatedby the inert porous separator.

In one embodiment, an ultracapacitor device comprising the carbonmaterial comprises a gravimetric power of at least 5 W/g, at least 10W/g, at least 15 W/g, at least 20 W/g, at least 25 W/g, at least 30 W/g,at least 35 W/g, at least 50 W/g. In another embodiment, anultracapacitor device comprising the carbon material comprises avolumetric power of at least 2 W/g, at least 4 W/cc, at least 5 W/cc, atleast 10 W/cc, at least 15 W/cc or at least 20 W/cc. In anotherembodiment, an ultracapacitor device comprising the carbon materialcarbon material comprises a gravimetric energy of at least 2.5 Wh/kg, atleast 5.0 Wh/kg, at least 7.5 Wh/kg, at least 10 Wh/kg, at least 12.5Wh/kg, at least 15.0 Wh/kg, at least 17.5. Wh/kg, at least 20.0 Wh/kg,at least 22.5 Wh/kg or at least 25.0 Wh/kg. In another embodiment, anultracapacitor device comprising the carbon material comprises avolumetric energy of at least 1.5 Wh/liter, at least 3.0 Wh/liter, atleast 5.0 Wh/liter, at least 7.5 Wh/liter, at least 10.0 Wh/liter, atleast 12.5 Wh/liter, at least 15 Wh/liter, at least 17.5 Wh/liter or atleast 20.0 Wh/liter.

In some embodiments of the foregoing, the gravimetric power, volumetricpower, gravimetric energy and volumetric energy of an ultracapacitordevice comprising the carbon material are measured by constant currentdischarge from 2.7 V to 1.89 V employing a 1.0 M solution oftetraethylammonium-tetrafluroroborate in acetonitrile (1.0 M TEATFB inAN) electrolyte and a 0.5 second time constant.

In one embodiment, an ultracapacitor device comprising the carbonmaterial comprises a gravimetric power of at least 10 W/g, a volumetricpower of at least 5 W/cc, a gravimetric capacitance of at least 100 F/g(@0.5 A/g) and a volumetric capacitance of at least 10 F/cc (@0.5 A/g).In one embodiment, the aforementioned ultracapacitor device is a coincell double layer ultracapacitor comprising the carbon material, aconductivity enhancer, a binder, an electrolyte solvent, and anelectrolyte salt. In further embodiments, the aforementionedconductivity enhancer is a carbon black and/or other conductivityenhancer known in the art. In further embodiments, the aforementionedbinder is Teflon and or other binder known in the art. In furtheraforementioned embodiments, the electrolyte solvent is acetonitrile orpropylene carbonate, or other electrolyte solvent(s) known in the art.In further aforementioned embodiments, the electrolyte salt istetraethylaminotetrafluroborate or triethylmethyl aminotetrafluroborateor other electrolyte salt known in the art, or liquid electrolyte knownin the art.

In one embodiment, an ultracapacitor device comprising the carbonmaterial comprises a gravimetric power of at least 15 W/g, a volumetricpower of at least 10 W/cc, a gravimetric capacitance of at least 110 F/g(@0.5 A/g) and a volumetric capacitance of at least 15 F/cc (@0.5 A/g).In one embodiment, the aforementioned ultracapacitor device is a coincell double layer ultracapacitor comprising the carbon material, aconductivity enhancer, a binder, an electrolyte solvent, and anelectrolyte salt. In further embodiments, the aforementionedconductivity enhancer is a carbon black and/or other conductivityenhancer known in the art. In further embodiments, the aforementionedbinder is Teflon and or other binder known in the art. In furtheraforementioned embodiments, the electrolyte solvent is acetonitrile orpropylene carbonate, or other electrolyte solvent(s) known in the art.In further aforementioned embodiments, the electrolyte salt istetraethylaminotetrafluroborate or triethylmethyl aminotetrafluroborateor other electrolyte salt known in the art, or liquid electrolyte knownin the art.

In one embodiment, an ultracapacitor device comprising the carbonmaterial comprises a gravimetric capacitance of at least 90 F/g, atleast 95 F/g, at least 100 F/g, at least 105 F/g, at least 110 F/g, atleast 115 F/g, at least 120 F/g, at least 125 F/g, or at least 130 F/g.In another embodiment, an ultracapacitor device comprising the carbonmaterial comprises a volumetric capacitance of at least 5 F/cc, at least10 F/cc, at least 15 F/cc, at least 20 F/cc, at least 25 F/cc, or atleast 30 F/cc. In some embodiments of the foregoing, the gravimetriccapacitance and volumetric capacitance are measured by constant currentdischarge from 2.7 V to 0.1 V with a 5-second time constant andemploying a 1.8 M solution of tetraethylammonium-tetrafluroroborate inacetonitrile (1.8 M TEATFB in AN) electrolyte and a current density of0.5 A/g, 1.0 A/g, 4.0 A/g or 8.0 A/g.

In one embodiment, the present disclosure provides ultracapacitorscomprising a carbon material as disclosed herein, wherein the percentdecrease in original capacitance (i.e., capacitance before beingsubjected to voltage hold) of the ultracapacitor comprising the carbonmaterial after a voltage hold period is less than the percent decreasein original capacitance of an ultracapacitor comprising known carbonmaterials. In one embodiment, the percent of original capacitanceremaining for an ultracapacitor comprising the carbon material after avoltage hold at 2.7 V for 24 hours at 65° C. is at least 90%, at least80%, at least 70%, at least 60%, at least 50%, at least 40%, at least30% at least 20% or at least 10%. In further embodiments of theforegoing, the percent of original capacitance remaining after thevoltage hold period is measured at a current density of 0.5 A/g, 1 A/g,4 A/g or 8 A/g.

In another embodiment, the present disclosure provides ultracapacitorscomprising a carbon material as disclosed herein, wherein the percentdecrease in original capacitance of the ultracapacitor comprising thecarbon material after repeated voltage cycling is less than the percentdecrease in original capacitance of an ultracapacitor comprising knowncarbon materials subjected to the same conditions. For example, in oneembodiment, the percent of original capacitance remaining for anultracapacitor comprising the carbon material is more than the percentof original capacitance remaining for an ultracapacitor comprising knowncarbon materials after 1000, 2000, 4000, 6000, 8000, or 1000 voltagecycling events comprising cycling between 2 V and 1V at a currentdensity of 4 A/g. In another embodiment, the percent of originalcapacitance remaining for an ultracapacitor comprising the carbonmaterial after 1000, 2000, 4000, 6000, 8000, or 1000 voltage cyclingevents comprising cycling between 2 V and 1V at a current density of 4A/g, is at least 90%, at least 80%, at least 70%, at least 60%, at least50%, at least 40%, at least 30% at least 20% or at least 10%.

As noted above, the carbon material can be incorporated intoultracapacitor devices. In some embodiments, the carbon material ismilled to an average particle size of about 10 microns using a jetmillaccording to the art. While not wishing to be bound by theory, it isbelieved that this fine particle size enhances particle-to-particleconductivity, as well as enabling the production of very thin sheetelectrodes. The jetmill essentially grinds the carbon against itself byspinning it inside a disc shaped chamber propelled by high-pressurenitrogen. As the larger particles are fed in, the centrifugal forcepushes them to the outside of the chamber; as they grind against eachother, the particles migrate towards the center where they eventuallyexit the grinding chamber once they have reached the appropriatedimensions.

In further embodiments, after jet milling the carbon is blended with afibrous Teflon binder (3% by weight) to hold the particles together in asheet. The carbon Teflon mixture is kneaded until a uniform consistencyis reached. Then the mixture is rolled into sheets using a high-pressureroller-former that results in a final thickness of 50 microns. Theseelectrodes are punched into discs and heated to 195° C. under a dryargon atmosphere to remove water and/or other airborne contaminants. Theelectrodes are weighed and their dimensions measured using calipers.

The carbon electrodes of the EDLCs are wetted with an appropriateelectrolyte solution. Examples of solvents for use in electrolytesolutions for use in the devices of the present application include butare not limited to propylene carbonate, ethylene carbonate, butylenecarbonate, dimethyl carbonate, methyl ethyl carbonate, diethylcarbonate, sulfolane, methylsulfolane and acetonitrile. Such solventsare generally mixed with solute, including, tetralkylammonium salts suchas TEATFB (tetraethylammonium tetrafluoroborate); TEMATFB(tri-ethyl,methylammonium tetrafluoroborate); EMITFB(1-ethyl-3-methylimidazolium tetrafluoroborate), tetramethylammonium ortriethylammonium based salts. Further the electrolyte can be a waterbased acid or base electrolyte such as mild sulfuric acid or potassiumhydroxide.

In some embodiments, the electrodes are wetted with a 1.0 M solution oftetraethylammonium-tetrafluroroborate in acetonitrile (1.0 M TEATFB inAN) electrolyte. In other embodiments, the electrodes are wetted with a1.0 M solution of tetraethylammonium-tetrafluroroborate in propylenecarbonate (1.0 M TEATFB in PC) electrolyte. These are commonelectrolytes used in both research and industry and are consideredstandards for assessing device performance. In other embodiments, thesymmetric carbon-carbon (C—C) capacitors are assembled under an inertatmosphere, for example, in an Argon glove box, and a NKK porousmembrane 30 micron thick serves as the separator. Once assembled, thesamples may be soaked in the electrolyte for about 20 minutes or moredepending on the porosity of the sample.

In some embodiments, the capacitance and power output are measured usingcyclic voltammetry (CV), chronopotentiometry (CP) and impedancespectroscopy at various voltages (ranging from 1.0-2.5 V maximumvoltage) and current levels (from 1-10 mA) on a Biologic VMP3electrochemical workstation. In this embodiment, the capacitance may becalculated from the discharge curve of the potentiogram using theformula:

$\begin{matrix}{C = \frac{I \times \Delta\; t}{\Delta\; V}} & {{Equation}\mspace{14mu} 1}\end{matrix}$where I is the current (A) and ΔV is the voltage drop, Δt is the timedifference. Because in this embodiment the test capacitor is a symmetriccarbon-carbon (C—C) electrode, the specific capacitance is determinedfrom:C _(s)=2C/m _(e)  Equation 2where m_(e) is the mass of a single electrode. The specific energy andpower may be determined using:

$\begin{matrix}{E_{s} = {\frac{1}{4}\frac{{CV}_{\max}^{2}}{m_{e}}}} & {{Equation}\mspace{14mu} 3} \\{P_{s} = {E_{s}\text{/}4{ESR}}} & {{Equation}\mspace{14mu} 4}\end{matrix}$where C is the measured capacitance V_(max) is the maximum test voltageand ESR is the equivalent series resistance obtained from the voltagedrop at the beginning of the discharge. ESR can alternately be derivedfrom impedance spectroscopy.

2. Batteries

The disclosed carbon materials also find utility as electrodes in anynumber of types of batteries. For example, one embodiment is directed toan electrical energy storage device comprising:

a) at least one anode comprising a carbon material;

b) at least cathode comprising a metal oxide; and

c) an electrolyte comprising lithium ions;

wherein the carbon material is any of the carbon materials describedherein.

Another embodiment is directed to a metal air battery, for examplelithium air batteries. Lithium air batteries generally comprise anelectrolyte interposed between positive electrode and negativeelectrodes. The positive electrode generally comprises a lithiumcompound such as lithium oxide or lithium peroxide and serves to oxidizeor reduce oxygen. The negative electrode generally comprises acarbonaceous substance which absorbs and releases lithium ions. As withsupercapacitors, batteries such as lithium air batteries which comprisethe disclosed carbon materials are expected to be superior to batteriescomprising known carbon materials. Accordingly, in one embodiment thepresent invention provides a metal air battery, for example a lithiumair battery, comprising a carbon material as disclosed herein.

Any number of other batteries, for example, zinc-carbon batteries,lithium/carbon batteries, lead acid batteries and the like are alsoexpected to perform better with the carbon materials described herein.One skilled in the art will recognize other specific types of carboncontaining batteries which will benefit from the disclosed carbonmaterials. Accordingly, in another embodiment the present inventionprovides a battery, in particular a zinc/carbon, a lithium/carbonbatteries or a lead acid battery comprising a carbon material asdisclosed herein.

EXAMPLES Example 1 Reaction Between Dried Resorcinol-FormaldehydePolymer Gel and Urea at Different Mass Ratios at 95 C

A monolithic, microporous dried polymer gel (formed from resorcinol,formaldehyde, and a volatile basic salt in the presence of a wateracetic acid co-solvent system as described previously) ground intoparticles by mortar and pestle. Separately, solid urea was ground bymortar and pestle. The dried polymer gel particles and urea particleswere then blended by mixing together in mortar and pestle at variousratios from 1:2 to 5:1 (polymer:urea, mass:mass). These solids blendswere then incubated for 24 h at 95 C. The samples are described in Table1.

TABLE 1 Description of samples for Example 1. Sample CompositionIncubation 1-1A 1:2 Dried polymer gel:Urea None 1-1B 1:2 Dried polymergel:Urea 24 h at 95 C. 1-2A 1:1 Dried polymer gel:Urea None 1-2B 1:1Dried polymer gel:Urea 24 h at 95 C. 1-3A 2:1 Dried polymer gel:UreaNone 1-3B 2:1 Dried polymer gel:Urea 24 h at 95 C. 1-4A 5:1 Driedpolymer gel:Urea None 1-4B 5:1 Dried polymer gel:Urea 24 h at 95 C.

The FTIR in the region of ˜1800 cm−1 to 800 cm−1 wavenumbers in shown inFIG. 1 for the sample at t=0 and after t=24 h incubation at 95 C for theratio of 1:2 dried polymer gel:urea. The spectra appear similar,indicating that the 1:2 ratio and temperature and time conditions werenot sufficient enough to impart any chemical changes in the material. Asimilar conclusion can be drawn from the FTIR of the samples produced atthe 1:1 ratio (FIG. 2). For the case of the 2:1 ratio (FIG. 3), therewere differences noted in the FTIR spectrum. For example, there wasadditional absorbance in the area at about 1660 cm−1, at about 1550 to1530 cm−1, and at about 1440 cm−1. Without being bound by theory, thesedifference in absorbance is due to chemical changes occurring resultingin new bonds formed or broken between the dried polymer gel and ureamaterials. For example, the 1660 cm−1 may be due to water evolution asproduct via condensation, and 1550 to 1530 cm−1, and 1440 cm−1absorbance due to formation of C—N bonds, for example primary orsecondary amine type. A similar observation was made for the 5:1 massratio of dried polymer gel:urea tested (FIG. 4). These data areconsistent with a chemical process that requires a sufficient amount ofone reactant (in this case, urea) to the other (in this case, driedpolymer gel).

Example 2 Time Course of Reaction Between 2:1 DriedResorcinol-Formaldehyde Polymer Gel:Urea at 95 C

A monolithic, microporous dried polymer gel (formed from resorcinol,formaldehyde, and a volatile basic salt in the presence of a wateracetic acid co-solvent system as described previously) was ground intoparticles by mortar and pestle. Separately, solid urea was ground bymortar and pestle. The dried polymer gel particles and urea particleswere then blended at 2:1 polymer gel:urea by mixing together in mortarand pestle incubated for various times and FTIR data collected. Thesamples are described in Table 2.

TABLE 2 Description of samples for Example 2. Sample CompositionIncubation 2-1 2:1 Dried polymer gel:Urea None 2-2 2:1 Dried polymergel:Urea 3 h at 95 C. 2-3 2:1 Dried polymer gel:Urea 12 h at 95 C. 2-42:1 Dried polymer gel:Urea 72 h at 95 C.

The FTIR in the region of ˜1800 cm−1 to 800 cm−1 wavenumbers in shows inFIG. 5. As can be seen, with increasing time there was increasingevidence for chemical change in the material, for example, withincreasing time at 95 C there were additional absorbance in the area atabout 1660 cm−1, at about 1550 to 1530 cm−1, and at about 1440 cm−1.These data are consistent with a chemical process occurring over time.

Example 3 Reaction Between Resorcinol-Formaldehyde Polymer Gel and Ureaat Different Mass Ratios at 95 C

A monolithic, microporous polymer gel (formed from resorcinol,formaldehyde, and a volatile basic salt in the presence of a wateracetic acid co-solvent system as described previously) was ground intoparticles by mortar and pestle. Separately, solid urea was ground bymortar and pestle. The polymer gel particles and urea particles werethen blended by mixing together in mortar and pestle at various ratiosfrom 1:2 to 5:1 (polymer:urea, mass:mass). These solids blends were thenincubated for 24 h at 95 C. The samples are described in Table 3.

TABLE 3 Description of samples for Example 1. Sample CompositionIncubation 3-1A 1:2 Polymer gel:Urea None 3-1B 1:2 Polymer gel:Urea 16 hat 95 C. 3-2A 1:1 Polymer gel:Urea None 3-2B 1:1 Polymer gel:Urea 16 hat 95 C.

The FTIR in the region of ˜1800 cm−1 to 800 cm−1 wavenumbers in shown inFIG. 6. The spectra show that following the 16 h incubation at 95 C,there was come change observed in the FTIR spectra, for example anincrease in absorbance in the area of about 1540 cm−1 and 1440 to 1400cm−1. These findings are consistent with Example 1 and 2, anddemonstrate that the both polymer gel (non-dried) and dried polymer gelare capable of reacting with the urea in the solid state. In this casethere was no change observed in the region of about 1660 cm−1, however,this finding is expected since in this case, the non-dried polymer gelhas a large water content, so any minor amounts of additional watergenerated in the system would not be expected to be detectable over thelarge amount already present.

Example 4 Pyrolysis of Solid-State Reacted Dried Polymer Gel:Urea andElectrochemical Characterization of Same

The solid state reacted dried polymer gel:urea according to sample 2-4(specifically 2:1 dried polymer gel:urea reacted for 72 h at 95 C) waspyrolyzed by heating to 1100 C and holding for 60 min under inertatmosphere (nitrogen flow). The resulting material (denoted sample 4-1)was characterized for nitrogen sorption. By this method, the specificsurface area was 7.4 m2/g, and the total pore volume was not detectable.

Electrochemical characterization for capacity in the presence of LiPF₆electrolyte was carried out as follows. An organic slurry was createdfrom a composition of 90:5:5 carbon:conductivity enhancer (SuperP):poly(vinylidene fluoride) by suspension in 1-methyl-2-pyrrolidinonevia mortar and pestle mixing. The suspension was coated onto a copperfoil substrate via doctor blade, calendared and dried for 1.5 h at 195C. This electrode was then assembled into a coin cell comprised of 316 LStainless Steel case (CR2032 geometry) with the copper providing theanode, lithium metal as counter electrode (cathode), a separator(Celgard 2325) and with 1M LiPF6 in 1:1 w/w Ethylene carbonate/Diethylcarbonate as electrolyte. The electrochemical testing protocol wascomprised of an asymmetric* constant current constant voltage 5 hourhold @ 0.005V, a voltage window of 2V-0.005V (vs. Li/Li+), and currentdensity of 40 mA/g, and this cycle of charge and discharge was repeatedfor at least two cycles.

The capacity data are summarized in Table 4. As can be seen, sample 3-1had about 65% first cycle efficiency with a capacity of about 360-370mAh/g after several cycles.

TABLE 4 Capacity data for sample 4-1. Cycle Extracted (mAh/g) Inserted(mAh/g) Efficiency (%) 1 296 455 65 2 324 344 94 3 341 354 96 4 353 36497

Example 5 Co-Pyrolysis of Dried Polymer Gel:Urea and ElectrochemicalCharacterization of Same

For this example, sample 5-1 was created by co-pyrolysis of a mixture of1:1 dried microporous polymer gel (formed from resorcinol, formaldehyde,and a volatile basic salt in the presence of a water acetic acidco-solvent system as described previously):urea (w:w). The material wasmixed via mortar and pestle and subsequently this mixture was pyrolyzedby heating to 1100 C at 10 C/min and held for 60 min under inertatmosphere (nitrogen flow). As a control, a second sample was generatedthat was pyrolyzed in the absence of any urea. The resulting materialswere characterized for nitrogen sorption and also for electrochemicalcharacterization employing the same methods as for Example 4. The dataare summarized in Table 5. As can be seen, the co-pyrolysis in thepresence of urea resulted in dramatic decrease in carbon surface areaand increase in electrochemical performance in the LiPF₆ electrolytesystem.

TABLE 5 Characterization of Samples 5-1 and 5-2. SpecificElectrochemical Performance Surface Pore Effi- Area Volume ExtractedInserted ciency Sample (m2/g) (cm3/g) Cycle (mAh/g) (mAh/g) (%) 5-1 2630.14 1 385 590 65 (co- pyrolyzed dried polymer:urea 1:1) 5-2 491 0.21 1227 406 56 (control)

Example 6 Pyrolysis of Solid-State Reacted Dried PolymerGel:Hexamethylenetetramine and Electrochemical Characterization of Same

A solid state reaction was carried out as follows. Dried microporouspolymer gel (formed from resorcinol, formaldehyde, and a volatile basicsalt in the presence of a water acetic acid co-solvent system asdescribed previously) was mixed via mortar and pestle withhexamethylenetetramine at a ratio of 1:1 dried polymergel:hexamethylenetetramine (w:w) and incubated at 140 C for 96 h. Theresulting material (denoted sample 6-1) was characterized for nitrogensorption. By this method, the specific surface area was 0.13 m2/g, andthe total pore volume was not detectable.

Electrochemical characterization for capacity in the presence of LiPF6electrolyte was carried out per methods described in Examples 4 and 5.The capacity data are summarized in Table 6. As can be seen, sample 6-1had about 69% first cycle efficiency with a capacity of about 360-370mAh/g after several cycles.

TABLE 6 Capacity data for sample 6-1. Cycle Extracted (mAh/g) Inserted(mAh/g) Efficiency (%) 1 291 420 69 2 339 363 93 3 352 363 97 4 354 36198

Example 7 Solid-State Reacted Pyrolyzed Carbon:Hexamethylenetetramineand Electrochemical Characterization of Same

A solid state reaction was carried out as follows. Pyrolyzed mesoporouscarbon (formed from pyrolysis of a polymer gel comprised of resorcinol,formaldehyde, and a volatile basic salt in the presence of a wateracetic acid co-solvent system as described previously) was mixed viamortar and pestle with hexamethylenetetramine at a ratio of 1:1pyrolyzed carbon:hexamethylenetetramine (w:w) and incubated at 140 C for13 to 96 h. After the treatment with hexamethylenetetramine, thepyrolyzed carbon was re-pyrolyzed consistent with the above examples.The resulting material (denoted sample 6-1) was characterized fornitrogen sorption, and compared to a control (non hexamethylenetetraminetreated). Electrochemical characterization for capacity in the presenceof LiPF6 electrolyte was carried out per methods described above. Thedata are summarized in Table 7. As can be seen, the HMT treatment ofpyrolyzed carbon allowed for high capacity in the resulting carbon up to1300 mAh/g capacity on first cycle, with first cycle efficiency in therange of 50-55%.

TABLE 7 Characterization of Samples 7-1, 7-2, and 7-3. Specific SurfacePore Electrochemical Performance Area Volume Extracted InsertedEfficiency Sample (m2/g) (cm3/g) Cycle (mAh/g) (mAh/g) (%) 7-1 ND ND 1590 1101 54 (13 h 2 564 606 93 solid-state reacted) 7-2 588 0.62 1 6551322 50 (72 h solid 2 ND 675 ND state reacted) 7-3 697 0.67 ND ND ND ND(control) ND = not determined.

Example 8 Solid-State Reaction Between Various Compounds

Various compositions were produced using the following solid materials:bisphenol A as a polymer precursor, hexamethylenetetramine as thecrosslinker, oxalic acid as an acid, and Tris(hydroxymethyl)aminomethane(Tris) as a base. The compositions can be described in terms of themolar ratios of the crosslinker to precursor, precursor to acid andprecursor to base.

TABLE 8 Description of samples for Example 8. Cross- Sam-linker:Precursor Precursor:Acid Precursor:Base ple (mol:mol) (mol:mol)(mol:mol) Incubation 8-1A 1.63 ∞ ∞ None (no acid) (no base) 8-1B 1.63 ∞∞ 6 h at 130 C. (no acid) (no base) 8-2A 1.63 1.00 5.00 None 8-2B 1.631.00 5.00 6 h at 130 C. 8-3A 1.63 10.0 5.0 None 8-3B 1.63 10.0 5.0 6 hat 130 C. 8-4A 1.63 100.0 5.0 None 8-4B 1.63 100.0 5.0 6 h at 130 C.8-5A 1.63 1.0 100.0 None 8-5B 1.63 100.0 100.0 6 h at 130 C. 8-6A 1.63100.0 100.0 None 8-6B 1.63 100.0 100.0 6 h at 130 C. 8-7A 2.00 10.0 5.0None 8-7B 2.00 10.0 5.0 6 h at 130 C. 8-8A 0.81 10.0 5.0 None 8-8B 0.8110.0 5.0 6 h at 130 C.

The FTIR spectra for samples 8-1A and 8-1B are depicted in FIG. 7. Ascan be seen, there was little to no change observed in the spectrum,indicating little or no change in chemical bonding in the material.Therefore, without being bounded by theory, it is concluded under theseconditions that no polymerization (or other chemical process for thatmatter) had occurred.

In contrast, the FTIR spectra for samples 8-2A and 8-2B (FIG. 8) showsignificant differences, indicating a change in chemical bonds thatwould be consistent with reaction (i.e., polymerization) between thevarious materials blended. For the various other cases, there werevarying degrees of differences in FTIR spectra observed, indicatingvarying degrees of reaction occurring, demonstrating the ability to tuneand control the reaction via judicious selection of the composition. Forexample, there was also significant chemical changes observed betweensample 8-5A and 8-5B (FIG. 11), some minor changes observed betweensample 8-6A and 8-6B (FIG. 12), and lesser to minimal changes observedbetween sample 8-3A and 8-3B (FIG. 9), between sample 8-4A and 8-4B(FIG. 10), between sample 8-7A and 8-7B (FIG. 13) and between sample8-8A and 8-8B (FIG. 14).

Example 9 Pyrolysis of Samples Described in Example 8

The samples denoted with a “B” from the previous example (Example 8)were pyrolyzed at 900 C under nitrogen gas flow. In addition topyrolysis by placing the material into a kiln at 900 C and holding for60 min, and then removed, a second approach (denoted “Slow”) wasexplored where the material was loaded into a tube furnace at roomtemperature and then heated to 900 at a ramping rate of typically 10C/min, held for 60 min and then ramped back down to room temperature.

The resulting data for weight loss and nitrogen sorption are presentedin Table 9.

TABLE 8 Description of samples for Example 9 and associated data.Pyrolysis Yield Specific Surface Pore Volume Sample Description (%) Area(m2/g) (cm3/g) 9-1A Pyrolyzed 25 665 0.256 Sample 8-1B 9-1B “Slow” 0 — —Pyrolyzed 8-1B 9-2A Pyrolyzed 0 — — Sample 8-2A 9-2B Pyrolyzed 11 7480.300 Sample 8-2B 9-2C “Slow” 27 <1 <1 Pyrolyzed 8-2B 9-3 Pyrolyzed 25572 0.225 Sample 8-3B 9-4 Pyrolyzed 22 548 0.214 Sample 8-4B 9-5APyrolyzed 13 968 0.388 Sample 8-5B 9-5B “Slow” 28 <1 <1 Pyrolyzed 8-5B9-6 Pyrolyzed 26 570 0.222 Sample 8-6B 9-7 Pyrolyzed 24 588 0.235 Sample8-7B 9-8 Pyrolyzed 29 545 0.215 Sample 8-8B

For sample 9-1A, it was found the even though no chemical change wasobserved for the sample, pyrolysis resulted in a pyrolyzed carbon at 25%yield. This result is unexpected since the material was comprised ofrelatively low molecular weight species that would be expected to notsurvive the pyrolysis conditions. Without being bound by theory, thematerials underwent chemical rearrangement (i.e., polymerization) duringheating in the kiln. It is important to note that pyrolysis under “slow”conditions (Sample 9-1B) resulted in the expected zero yield (nopyrolyzed carbon obtained).

For sample 9-2A vs. 9-2B, it was observed that the sample that was notincubated at the previous condition of 6 h at 130 C did not yield anypyrolyzed carbon upon pyrolysis. Furthermore, when sample 8-2B waspyrolyzed under slow condition to yield sample 9-2C, a pyrolyzed carbonmaterial was obtained, but had no surface area or pre volume detected bynitrogen sorption. A similar observation was made for sample 9-5B vs.9-5A.

The pore distribution for the various samples appeared to be microporousin nature. An example pore distribution plot is show in FIG. 15 forsample 9-5A.

Example 10 Activation of Pyrolyzed Carbon Samples Described in Example 9and Electrochemical Characterization

Selected pyrolyzed carbon samples from Example 10 were activated at 900C under carbon dioxide gas flow. The data are summarized in Table 9.

TABLE 9 Description of samples for Example 9 and associated data.Activation Specific Pore Nitrogen Rate Surface Area Volume sorbed SampleDescription (%/min) (m2/g) (cm3/g) P₉₅/P₀₅ 10-1 Activated 0.119 13170.528 1.06 Sample 9-1A 10-2 Activated 0.148 1588 0.652 1.11 Sample 9-2B10-3 Activated 0.161 1573 0.64 1.09 Sample 9-5A 10-4 Activated 0.1121114 0.44 1.04 Sample 9-5B

The pore distribution for the various samples appeared to be microporousin nature. An example pore distribution plot is show in FIG. 16 forsample 10-3.

Sample 10-3 was also examined for electrochemical performance,specifically, capacitance and performance in an EDLC and in anelectrolyte system comprised of TEATFB in acetonitrile. The methods forelectrode and ultracapacitor construction and electrochemical testingare consistent with methods described herein. This activated carbon wasfound to have a volumetric capacitance of 24.3 F/cc, a maximumtheoretical volumetric capacitance of 27.2 F/cc, and a gravimetriccapacitance of 118 F/g.

Example 11 Electrochemical Performance of Carbon Treated withHexamethylenetetramine

A microporous activated carbon (sample 11-1) was obtained via pyrolysisand activation of a crushed polymer gel monolith, and jet milled (toDv,50 of 7.15 um) as previously described. This carbon was thenphysically mixed via mortar and pestle with hexamethylenetetraminepowder in a 1:1 (mass:mass) ratio, and the blended mixture was stored at140 C for 96 H. Following this incubation, the HMT-treated carbon washeld in the presence of an inert atmosphere (flowing nitrogen gas) andheated to 900 C and cooled back to room temperature. The resultingHMT-treated carbon is denoted 11-2. The physicochemical data for the twocarbons are presented in Table 10 and electrochemical data shown inTable 11.

TABLE 10 Physicochemical data for carbons for Example 11. SpecificSurface Area Pore Volume SSA/PV Sample Description (m2/g) (cm3/g) (GM)11-1 Microporous activated 1709 0.730 23.4 carbon 11-2 Microporousactivated 1411 0.601 23.5 carbon treated with hexamethylenetetramine for96 h at 140 C. 11-3 Microporous activated 1450 0.603 24.0 carbon atlower activation level

TABLE 11 Electrochemical data for carbons for Example 11. MaximumGravimetric Theoretical Capacitance Capacitance Resistance (Ohm) Sample(F/g) (F/cc) R1 R2 11-1 112.8 24.2 3.19 3.15 11-2 103.1 24.8 4.05 3.5411-3 105.9 25.4 6.93 3.84

As can be seen, the treatment with hexamethylenetetramine resulted in adecrease in carbon surface area, with a decrease in gravimetriccapacitance. For comparison of electrochemical performance, anothermicroporous activated carbon was examined (Sample 11-3), with a similarsurface area to the hexamethylenetetramine treated carbon (sample 11-2).It can be seen, that the hexamethylenetetramine treated carbon exhibiteda much lower resistance than the comparator at the similar surface area.

Example 12 Solid State Polymerization of Glucose

A mass of 10 grams of D-glucose powder was placed in an alumina crucibleand heated in air in a convection oven at 140 C for 2 hours. During thistime, the glucose melted, became golden in color, and solidified. Theresulting resin was crushed and characterized via FT-IR (data shown inFIG. 17) and BET nitrogen adsorption (data shown in Table 12).Alternatively, the temperature can be increased or decreased to yield ahigher or lower cross-linked resin, respectively. The resulting resinwas pyrolyzed at 900 C for 1 h in a tube furnace under nitrogen flow.The resulting carbon was characterized via BET nitrogen adsorption (datashown in Table 12) and electrochemically tested in a coin cell vs.lithium metal with 1M LiPF6 in 1:1 w/w EC:DEC electrolyte via constantcurrent discharge/charge cycling. The voltage profile is shown in FIG.18.

TABLE 12 BET nitrogen adsorption data for glucose resin and carbon forExample 12. BET Specific Surface Area Phase (m²/g) BET Pore Volume(cm³/g) Carbon 39 0.008 Resin <1 <1

Example 13 Solid State Polymerization of Fructose

A mass of 10 grams of fructose powder was placed in an alumina crucibleand heated in air in a convection oven at 140 C for 48 hours. Duringthis time, the fructose melted, became brown in color, and solidified.The resulting resin was crushed and characterized via FT-IR (data shownin FIG. 19) and BET N2 adsorption (data shown in Table 13).Alternatively, the temperature can be increased or decreased to yield ahigher or lower cross-linked resin, respectively. The resulting resinwas pyrolyzed at 900 C for 1 hr in a tube furnace under nitrogen flow.The resulting carbon was characterized via BET nitrogen adsorption (datashown in Table 13) and electrochemically tested in a coin cell vs.lithium metal with 1M LiPF6 in 1:1 w/w EC:DEC electrolyte via constantcurrent discharge/charge cycling between −0.015V-2V (vs. Li/Li+). Thevoltage profile is shown in FIG. 20.

TABLE 13 BET nitrogen adsorption data for fructose resin and carbon forExample 13. BET Specific Surface Area Phase (m²/g) BET Pore Volume(cm³/g) carbon 333 0.163 resin <1 <1

Example 14 Hard Carbon Anode-Solid State Reaction Examples forMelamine-Glucose-Ammonium Di-Hydrogen Phosphate Resin

In a mortar and pestle, 3.1 grams of melamine was ground together with2.2 grams of D-Glucose for 15 minutes. Next, 1.0 gram of Ammoniumdi-hydrogen Phosphate was added to the mixture and it was continuallycrushed and mixed for 20 minutes. The solid white mixture was thenpoured into a crucible and placed in a 120C oven for 24 hours. Thetemperature was then increased to 140 C and the sample was held for 6hours. The resulting resin was a brown solid mass. After the 140C hold,the sample was pyrolyzed at 1050 C for 1 hour using a Thermo Scientific,Economy Solid Tube furnace. The resulting carbon was then tested forspecific surface area and pore volume using a Micromeritics Tristar IIBET system. Nitrogen isotherm, surface area, and pore volume data isshown in FIG. 21 and Table 14.

TABLE 14 BET nitrogen adsorption data for Example 14. Nitrogen sorbedTrue Density Sample SSA (m²/g) PV (cm³/g) P₉₅/P₀₅ (g/cm³) 14-1 173 0.0861.18 1.9582

Example 15 Hard Carbon Anode-Solid State Reaction Examples forMelamine-Glucose-Ammonium Di-Hydrogen Phosphate Resin

In a mortar and pestle, 1.65 grams of melamine was ground together with2.36 grams of D-Glucose for 15 minutes. Next, 2.0 gram of Ammoniumdi-hydrogen Phosphate was added to the mixture and it was continuallycrushed and mixed for 20 minutes. The solid white mixture was thenpoured into a crucible and placed in a 120C oven for 24 hours. Thetemperature was then increased to 140 C and the sample was held for 6hours. The resulting resin was a brown solid mass. After the 140C hold,the sample was pyrolyzed at 1050 C for 1 hour using a Thermo Scientific,Economy Solid Tube furnace.

Example 16 Hard Carbon Anode-Solid State Reaction Examples forMelamine-Glucose-Ammonium Di-Hydrogen Phosphate Resin

In a mortar and pestle, 1.26 grams of melamine was ground together with1.80 grams of D-Glucose for 15 minutes. Next, 3.0 gram of Ammoniumdi-hydrogen Phosphate was added to the mixture and it was continuallycrushed and mixed for 20 minutes. The solid white mixture was thenpoured into a crucible and placed in a 120C oven for 24 hours. Thetemperature was then increased to 140 C and the sample was held for 6hours. The resulting resin was a brown solid mass. After the 140C hold,the sample was pyrolyzed at 1050 C for 1 hour using a Thermo Scientific,Economy Solid Tube furnace.

Example 17 Solid State Reaction 2-Naphthol and Examples forMelamine-Glucose-Ammonium Di-Hydrogen Phosphate Resin

In a mortar and pestle, a 1:1 mass ratio of 2-naphthol andhexamethylenetetramine was ground together and held at 130 C for about12 h. The resulting material was “slow” pyrolyzed as described above.This resulted in a pyrolyzed carbon at 27% yield (sample 17-1). Thesingle point surface area by nitrogen sorption was 1.5 m2/g. The poredistribution was found to include micro and mesopores (FIG. 22).

Example 18 Polymerization of Precursor Compounds in a Kiln

The monomer or precursor compounds to be polymerized in this example canbe selected from the various species described herein. The particle sizereduction of the various species can be accomplished as known in theart, for example (but not limited to) by ball milling, jet milling,grinding, sieving, and the like, and combination thereof. In certainembodiments the particle size of the materials is manipulated to controlthe polymerization by altering the relative amount of each material thatis allowed to mix locally. After particle size reduction, an alternatecatalyst can be combined, for example an acid or a base, or combinationsthereof. The mixture can be loaded into a kiln, or other reactor capableof heating and/or mixing solids in at elevated temperature withcontrolled flow of gas. For instance, the power mixture can be loadedinto a continuous throughput rotary kiln hopper. The kiln can be purgedwith nitrogen. When the kiln reaches steady state, the mixture can beintroduced into the kiln at a predetermined rate. The first zone of thekiln can be set to 150 C (change to appropriate temperature as needed)and the feed rate, rotation and kiln angle set to allow the material toreside in the first hot zone for 30 minutes. While not wishing to bebound by theory it is expected that the material in the first hot zoneis melted and then polymerized before passing into the second and thirdhot zone where pyrolysis occurs. The second zone of the kiln can be setto 500 C and the last zone set to 800 C. In certain embodiments thepolymerization takes place in one kiln where temperatures appropriatefor polymerization are used as set points (50 C-300 C) and pyrolysistakes place in a second kiln where temperature appropriate for pyrolysisare used as set points (300 C-1100 C). More the two, for example 3 or 4or 5 or more different heating zones can be employed. Different reactiongases can be introduced into each zone. The exiting pyrolyzed materialcan be collected in a hopper. In various embodiments of this example,the particles size (Dv,50) can range from 1 um to 10 cm, for example 1um to 2 cm, for example from 1 um to 50 um, for example from 100 um to 2mm. In various embodiments, alternate milling techniques can includeFrisch mill, Jet mill, ball mill, roller mill, fluidized jet mill.

Example 19 Preparation of Polymers from a Precursor System Comprised ofBPA and HMT at Various Ratios, and Production and Characterization ofCarbon Produced from Same

Various polymeric materials were produced by mixing solid bisphenol A(BPA) and solid hexamethylenetetramine (HMT) at various ratios, andincubating the solid, solvent-free mixture for various times (14 h to 16h) and temperatures (130-140 C) as described in Table 15. The meltingpoint of BPA is 158 C. These polymers were pyrolyzed and activatedgenerally according to the procedures described herein. Properties ofthe resulting activated carbons are described in Table 16, including theconversion ratio, which is defined as the mass units of precursorsrequired to achieve one mass unit of carbon, and the normalizedconversion ratio, which the mass units of precursors required to achieveone mass unit of carbon normalized to a carbon surface area of 1700m2/g. The carbons produced were highly microporous, as evidenced by thevalues of % micropores, % mesopores, and % macropores listed in Table16. As can be seen, the lowest conversion factors, indicating the leastamount of precursor material required to produce a given mass of carbonmaterial occurs between about 2.5:1 to 0.166:1 HMT:BPA (mol:mol),preferably between about 1.63:1 to 0.668:1 HMT:BPA (mol:mol). Withoutbeing bound by theory, the HMT molecule provides 6 mol of formaldehyde(and 6 mol of ammonia) per mol whereas BPA has four primary potentialcross-linking sites (and other minor potential crosslinking sites),providing a stoichiometry of 2:3, or 0.667 mol:mol.

TABLE 15 Description of various polymer samples produced according toExample 19. Ratio HMT:BPA Temperature Time Oven yield Sample (mol:mol)(C.) (h) (%) 19-1 5:1 130 14 96 19-2 4:1 130 14 97 19-3 3:1 130 14 9319-4 2.5:1   130 14 93 19-5 1.63:1   130 14 94 19-6 1:1 130 14 95 19-70.668:1    140 16 93 19-8 0.166:1    140 16 98 19-9 0.050:1    140 16100

TABLE 16 Properties of various carbon samples produced according toExample 19. Micropores/ Surface Pore Mesopores/ Normalized Carbon AreaVolume Macropores Conversion Conversion Sample (m2/g) (cm3/g) (%/%/%)Ratio Ratio 19-1 1847 0.77 97.8/2.2/0 7.1 6.7 19-2 1819 0.756 98.2/1.8/08.8 8.4 19-3 1600 0.661  100/0/0 6.5 6.9 19-4 1673 0.692  100/0/0 5.65.6 19-5 1645 0.681 99.9/0.1/0 6.0 6.1 19-6 1692 0.700 99.7/0.3/0 5.85.8 19-7 1494 0.618  100/0/0 8.9 5.1 19-8 1048 0.436  100/0/0 4.4 5.719-9 864 0.35  100/0/0 4.7 11.0

Example 20 Preparation of Polymers from a Precursor System Comprised ofBPA, HMT and Oxalic Acid, and Production and Characterization of CarbonProduced from Same

Various polymeric materials were produced by mixing solid bisphenol A(BPA), solid hexamethylenetetramine (HMT), and solid oxalic acid (eitherdihydrate or anhydrous form) and incubating the solid, solvent-freemixture for 7 h at 130 C; the ratio of precursors is described in Table17. The melting point of oxalic acid is 101-102 C. These polymers werepyrolyzed and activated generally according to the procedures describedherein. Properties of the resulting activated carbons are described inTable 18. The carbons produced were highly microporous, as evidenced bythe values of % micropores, % mesopores, and % macropores listed inTable 18. The conversion factors (as defined above) were 5.7, 7.2, and6.3 for carbon samples 20-1, 20-2, and 20-3, respectively. Carbonsamples 20-1 and 20-3 were examined for their electrochemical propertiesin an EDLC generally employing the procedures described herein. Themeasured volumetric capacitances were 26.3 F/cc and 26.2 F/cc for carbonsamples 20-1 and 20-3, respectively. electrochemical properties in anEDLC generally employing the procedures described herein. The measuredgravimetric capacitances were 116.0 F/g and 26.2 F/cc for carbon samples20-1 and 20-3, respectively. For comparison, a commercial carbon, YP-50,was also tested and as can be seen the initial volumetric capacitance ofcarbon samples 20-1 and 20-3 were far greater (FIG. 23). Thissuperiority in volumetric capacitance was also maintained after a stresstest of the capacitors by a 3 V voltage hold for 12 hours at 65 C (seeFIG. 24). It was noted that the sample produced from the precursorsystem comprising HMT, BPA and oxalic acid (20-3), exhibited 86.3%retention of F/g compared to the sample produced from the precursorsystem comprising HMT and BPA (20-1), which exhibited 80.1% F/gretention. These data demonstrate how the invention herein is capable ofachieving extraordinarily high volumetric capacitance for carbon atbaseline and also after stress testing at 3V and elevated temperature inthe EDLC based on the TEATFB/acetonitrile system.

TABLE 17 Description of various polymer samples produced according toExample 20. Sample Composition 20-1 1.64:1 HMT:BPA (mol:mol) 20-21.64:1:1 HMT:BPA:oxalic acid dihydrate (mol:mol:mol) 20-3 1.64:1:1HMT:BPA:oxalic acid anhydrous (mol:mol:mol)

TABLE 18 Properties of various carbon samples produced according toExample 20. Micropores/ Surface Pore Mesopores/ Carbon Area VolumeMacropores Max Th Sample (m2/g) (cm3/g) (%/%/%) F/g F/cc F/cc 20-1 12810.552 96.3/1.7/2.0 116.0 26.3 29.4 20-2 1658 0.684 99.0/1.0/0 122.3 24.627.2 20-3 1416 0.584 100/0/0 119.2 26.2 29.1

Example 21 Electrochemical Characterization of Various Carbons

A variety of carbon samples were produced from either a binary precursorsystem comprised of BPA and HMT or a ternary precursor system comprisedof BPA, HMT, and oxalic acid. A plot of the maximum theoretical F/cc asa function of carbon surface area is presented in FIG. 25. As can beseen, there was a trend for increasing maximum theoretical volumetriccapacitance with decreasing surface area. A plot of the F/g as afunction of carbon total pore volume is presented in FIG. 26. As can beseen, there was a trend for increasing gravimetric capacitance withincreasing pore volume.

Example 22 Preparation of Carbon Materials Employing Solvent-FreeProcess

A monolithic, microporous polymer was formed using powder precursormaterials. Exemplary raw materials in this regard are bisphenol A asmonomer and hexamethylenetetramine as cross linking agent. The ratio ofbisphenol A to hexamethylenetetramine was varied from 1:1 to 5:1. Incertain instances, oxalic acid was added at a mol ratio of 1.63:1hexamethylenetetramine:oxalic acid.

The powder mixtures were incubated at 140 C for varying time periods,for example overnight (corresponding to 18 hours). Over this period, thepowders formed a polymer monolith. The polymer monolith was pyrolyzedand activated according to methods described elsewhere in theSpecifications.

Example 23 Preparation of Activated Carbon from Monolithic Polymer Resin

In this example, a monolithic microporous dried polymer gel (formed fromresorcinol, formaldehyde, and a volatile basic salt in the presence of awater acetic acid co-solvent system as described previously) is reactedin a hotbox oven set to 90° C. This is size reduced via a rock crusherand solvent removed using a lyophilization process.

A pyrolyzed carbon from this sample is fed into a rotary kiln systemunder inert atmosphere (nitrogen gas flow) at range of 600-800° C. Thispyrolyzed carbon was fed into a fluidized bed reactor and heated underinert nitrogen atmosphere to 880° C. and then exposed to reactive carbondioxide atmosphere. The carbon was cooled under nitrogen once thedesired specific surface area was achieved.

The granular activated carbon was fed into an 8″ Jet Mill and milled.The surface area was 1819 m2/g, the pore volume 0.763 cm3/g, the tapdensity was 0.66 g/cm3.

Example 24 Preparation of Activated Carbon with High Nitrogen Content

Solid state reacted materials using a nitrogen-containing cross-linkerlike Hexamethylenetetramine produce activated carbon materials in the1-4% of total mass in the final carbon form.

Activated and pyrolyzed carbon materials are produced with even highernitrogen contents by solid state reacting with nitrogen-containingchemicals such as urea and hexamethylenetetramine. Pyrolyzed andactivated carbons described in Example 22 were mixed with anitrogen-containing chemicals with a mortar and pestle in a 1:1 by massratio. This mixture was heated in an oven set to 130° C. for 12-24hours. The resulting material was then treated in a tube furnace at 800°C. under inert atmosphere (nitrogen gas flow) for 60 minutes.

Example 25 Nitrogen Content of Various Carbon Compositions

A range of carbon materials produced from the range of chemistries asdetailed in Example 22 and Example 23 were tested for Total NitrogenContent on a Perkin Elmer CHN Analyzer Model 2400. The samples aredescribed in Table 19.

TABLE 19 Description of various carbon samples of Example 25. NitrogenSample Content (%) Preparation Process 25-1 8.1% Carbon produced asdescribed in Example 22, carbon further treated as described in example24. 25-2 3.6% Carbon produced as described in Example 22 25-3 3.4%Carbon produced as described in Example 22 25-4 1.3% Carbon produced asdescribed in Example 22 25-5 0.9% Carbon produced as described inExample 23.

This example illustrates the approach for solid state reaction of HMT orother nitrogenous solid compounds with a solid carbonaceous material toincrease the nitrogen content of the carbonaceous materials. While notwishing to be bound by theory, it is believed that certain embodimentsof carbon materials prepared according to this manner comprisesubstantially all, (e.g., greater than 90% and up to greater than 95%)of the absorbed nitrogen on the outer surface of the carbon particleswhere it is more accessible to electrolyte, rather than within thecarbon particle where it would have substantially no contact withelectrolyte. One skilled in the art can employ this approach forincreasing nitrogen content of other carbonaceous materials, forexample, other forms of carbon including, but not limited to, amorphouscarbon, glassy carbon, hard carbon, graphite, graphene, other allotropesof carbon, and the like.

Example 26 Production of Carbon with Micro/Mesoporous Pore Structure ViaSolvent-Free Processing

A solid blend of 1:1:2 (mass:mass:mass) melamine:cyanuric acid:HMT wasmixed via mortar and pestle and heated to 140 C for 6 h. This materialwas pyrolyzed employing the procedures described herein. The resultingcarbon exhibited a surface area of 316 m2/g and a pore volume of 0.291cm3/g. The pore volume distribution for the resulting carbon (FIG. 27)was comprised of 56.1% micropores, 34.5 mesopores and 9.3% macropores.This example illustrates that carbons with substantial fraction of porevolume in the mesopore region may be produced employing the solvent-freemethodologies described herein.

Example 27 Production of Carbon with Micro/Meso/Macroporous PoreStructure Via Solvent-Free Processing

A solid blend of 1:1:1 (mass:mass:mass) cyanuric acid:HMT:urea was mixedvia mortar and pestle and heated to 140 C overnight. This material waspyrolyzed employing the procedures described herein. The resultingcarbon exhibited a surface area of 301 m2/g and a pore volume of 0.331cm3/g. The pore volume distribution for the resulting carbon (FIG. 28)was comprised of 35.2% micropores, 2.9% mesopores and 61.9% macropores.This example illustrates that carbons with substantial fraction of porevolume in the macropore region may be produced employing thesolvent-free methodologies described herein.

Example 28 One Step Preparation of Carbon from a Precursor SystemComprised of BPA, HMT and Oxalic Acid, and Characterization of Same

A solid blend of 2:1:1 (mass:mass:mass) BPA:HMT:oxalic acid dihydratewas mixed via shaking and placed into an alumina crucible. Sample 28-1was produced by heating the crucible at 10 C per min to 900 C and heldat 900 C for a dwell time of 360 min. A second sample (28-2) wasproduced by an analogous procedure except that the dwell time was 180min, and then the sample was cooled to room temperature, and then heateda second time at 10 C per min to 900 C and held for a dwell time of anadditional 180 min. Table 20 presents a summary of the carboncharacterization. As can be seen, the single step, solvent-free processto create activated carbon from solid precursors was capable ofproducing highly microporous, high capacitance carbon at excellentyield.

TABLE 20 Properties of various carbon samples produced according toExample 28. Surface Pore Micropores/ Normalized Max Carbon Area VolumeMesopores/Macropores Conversion conversion Th Sample (m2/g) (cm3/g)(%/%/%) factor factor F/g F/cc F/cc 28-1 1563 0.644 100/0/0 7.9 8.5 Notdetermined 28-2 1474 0.607 100/0/0 6.8 7.6 118.8 25.7 28.4

One skilled in the art can envision other pyrolysis reactorconfigurations that may be suitable to practice the current invention,for example, but not limited to rotary kiln, microwave kiln, pusher-typekiln, elevator kiln, fluidized bed reactor, and the like.

Example 29 Electrochemical Performance of Carbon in Slurry-BasedElectrode

Activated carbon (1800 m²/g surface area ad 0.77 cm3/g total porevolume) was produced from the ternary HMT:BPA:oxalic acid precursorsystem employing the solvent free process methodologies generallydescribed via slurry-based method as known in the art employing anelectrode formulation comprised of 90% active carbon, 5% conductivityenhancer, and 5% binder. The electrodes were assembled into an EDLC andelectrochemical performance measured at a current density of 0.5 Amp/gemploying an electrolyte comprising tetraethylammonium tetrafluoroboranein acetonitrile. The measured volumetric capacitance was 17.5 F/cc, thegravimetric capacitance was 120.8 F/g when normalized for the activecarbon material, and the maximum theoretical volumetric capacitance was25.0 F/cc as based on the pore volume of 0.77 cm3/g and the gravimetriccapacitance normalized for active carbon material. Following anincubation of 12 h at 3 V and 65 C, the retention in the F/g was 89%.For comparison, a commercial carbon, YP-50 was measured under the sameelectrode processing and electrochemical conditions. The YP-50 sampleexhibited 17.0 F/cc at baseline, and the F/g retention was only 80%after the same 12 h at 3V and 65 C condition. Therefore, carbon producedfrom HMT:BPA:oxaliac precursor system and solvent-free processingexhibit capacitance initially and a superior resistance to capacitancefade after the high voltage, high temperature exposure. Additionally, acyclic voltammetry sweep was conducted as known in the art for thecarbon of this example and the YP-50 commercial control carbon.

FIGS. 29A-D present results of the cyclic voltammetry In FIGS. 29A-D,“A” denotes the carbon of this example and “B” denotes YP-50. The Y axispresents current data in mA (−14 to 14 mA), while the X axis presentsvoltage data (either 0 to 2.7V or 0 to 3.0 V as described for eachfigure).

FIG. 29A shows the comparison for the two carbons cycled up to 2.7 V atthe initial baseline. FIG. 29B shows the comparison for the two carbonscycled up to 3.0 V at the initial baseline. FIG. 29C shows thecomparison for the two carbons cycled up to 2.7 V after the incubationat 12 h at 3 V and 65 C. FIG. 29D shows the comparison for the twocarbons cycled up to 3.0 V after the incubation at 12 h at 3 V and 65 C.In all circumstances, the carbon produced from HMT:BPA:oxaliac precursorsystem and solvent-free processing exhibits shows a more box-likestructure to the data. The “box-like” behavior is indicative of anefficient electric double layer capacitance (EDLC) effect, desirable forultracapacitors. The lower current response at higher voltages (˜3V)indicates greater stability and little to no charge transfer occurringto side reactions as opposed to the commercial carbon, which showsincreasing current at higher voltage.

One method to quantitate the fit of the CV data to ideal box shape is tocalculate a “boxellation factor” (BF) which equals the difference of thecurrent at 90% max voltage and the current at 10% max voltage divided bythe current at 50% max voltage(BF=(i@0.9_(Vmax)−i@0.1_(Vmax))/i@0.5_(Vmax). For the control sample ofExample 29 (YP-50), the calculated BF at baseline was about 0.3 and 0.4at 2.7 V and 3 V, respectively, whereas for the carbon producedemploying the solvent free process and based on the HMT:BPA:oxaliac acidprecursors, the BF at baseline was about 0.1 and 0.1, respectively. Forthe control sample of Example 29, the calculated BF after the incubationat 12 h at 3 V and 65 C was about 0.6 and 0.7 at 2.7 V and 3 V,respectively, whereas for the carbon produced employing the solvent freeprocess and based on the HMT:BPA:oxaliac acid precursors, the BF afterthe incubation was about 0.1 and 0.1, respectively.

Accordingly, certain embodiments are directed to carbon materials havinglow boxellation factors. For example, in certain embodiments, the BF atbaseline is less than about 0.3, less than about 0.2, less than about0.15 or even less than about 0.1. In other embodiments, the BF after anincubation period as described above is less than about 0.5, less thanabout 0.4, less than about 0.3, less than about 0.2, less than about0.15 or even less than about 0.1. The BF of the carbon materials iscalculated and tested according to the above description.

The various embodiments described above can be combined to providefurther embodiments. All of the U.S. patents, U.S. patent applicationpublications, U.S. patent applications, foreign patents, foreign patentapplications and non-patent publications referred to in thisspecification and/or listed in the Application Data Sheet, including butnot limited to U.S. Provisional Application No. 61/786,074, filed Mar.14, 2013, are incorporated herein by reference, in their entirety.Aspects of the embodiments can be modified, if necessary to employconcepts of the various patents, applications and publications toprovide yet further embodiments. These and other changes can be made tothe embodiments in light of the above-detailed description. In general,in the following claims, the terms used should not be construed to limitthe claims to the specific embodiments disclosed in the specificationand the claims, but should be construed to include all possibleembodiments along with the full scope of equivalents to which suchclaims are entitled. Accordingly, the claims are not limited by thedisclosure.

The invention claimed is:
 1. A method for preparing a polymer,comprising physically blending a mixture of particles comprising polymerprecursors and aging the mixture at a temperature and for a timesufficient for the polymer precursors to react with each other and forma polymer gel, and wherein the mixture comprises less than 10% solventby weight, and the polymer precursors are monomers.
 2. The method ofclaim 1, wherein the mixture comprises less than 1% solvent by weight.3. The method of claim 1, wherein the mixture comprises less than 0.1%solvent by weight.
 4. The method of claim 1, wherein the temperature isat or above the glass transition temperature of one or more of thepolymer precursors.
 5. The method of claim 1, wherein the temperature isat or above the melting temperature of one or more of the polymerprecursors.
 6. The method claim 1, wherein the temperature is 30° C. ormore below the melting temperature of one or more of the polymerprecursors.
 7. The method of claim 1, wherein the polymer precursors areselected from an amine-containing compound, an alcohol-containingcompound and a carbonyl-containing compound.
 8. The method of claim 1,wherein the polymer precursors are selected from an alcohol, a phenolcompound, a polyalcohol, a sugar, an alkyl amine, an aromatic amine, analdehyde, a ketone, a carboxylic acid, an ester, melamine, a urea, anacid halide and an isocyanate.
 9. The method of claim 8, wherein thephenolic compound is phenol, resorcinol, naphthol, bisphenol A, or anycombination thereof.
 10. The method of claim 8, wherein the sugar isfructose, sucrose, glucose, or any combination thereof.
 11. The methodof claim 8, wherein the carboxylic acid is acetic acid, formic acid,oxalic acid, lactic acid, citric acid, or any combination thereof. 12.The method of claim 1, wherein the polymer precursors comprisehexamethylenetetramine.
 13. The method of claim 1, wherein the polymerprecursors comprise hexamethylenetetramine and bisphenol A.
 14. Themethod of claim 1, further comprising pyrolyzing the polymer gel in aninert atmosphere at temperatures ranging from 500° C. to 2400° C. toobtain pyrolyzed polymer gel particles.
 15. The method of claim 14,further comprising activating the pyrolyzed polymer gel particles toobtain activated polymer gel particles by a method comprising contactingthe pyrolyzed polymer gel particles with an atmosphere comprising carbondioxide, carbon monoxide, steam, oxygen, or combinations thereof, at atemperature may ranging from 800° C. to 1300° C.
 16. A method forpreparing a polymer, comprising physically blending a mixture ofparticles comprising polymer precursors and aging the mixture at atemperature and for a time sufficient for the polymer precursors toreact with each other and form a polymer gel, and wherein the mixturecomprises less than 10% solvent by weight, and the polymer precursorsare monomers comprising hexamethylenetetramine and bisphenol A presentat a mole ratio between 0.05:1 to 5:1, respectively.
 17. The method ofclaim 1, wherein the polymer precursors comprise cyanuric acid.